TW201529555A - Anthracene derivative and method for synthesizing the same - Google Patents
Anthracene derivative and method for synthesizing the same Download PDFInfo
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- DIIPDJWEGUCLFB-UHFFFAOYSA-N CC(C)(C)c(c(-c1c(cccc2)c2c(-c2ccccc2)c2c1cccc2)c1)ccc1-[n]1c2ccccc2c2c1cccc2 Chemical compound CC(C)(C)c(c(-c1c(cccc2)c2c(-c2ccccc2)c2c1cccc2)c1)ccc1-[n]1c2ccccc2c2c1cccc2 DIIPDJWEGUCLFB-UHFFFAOYSA-N 0.000 description 1
- CLANWCJTTFZQFF-UHFFFAOYSA-N Cc(c(-c1c(ccc(-c2c(c3ccccc3[n]3-c(cc4)c(cccc5)c5c4-c4c(cccc5)c5c(-c5ccccc5)c5c4cccc5)c3ccc2)c2)c2c(-c2ccccc2)c2c1cccc2)c1)ccc1-[n]1c(cccc2)c2c2c1cccc2 Chemical compound Cc(c(-c1c(ccc(-c2c(c3ccccc3[n]3-c(cc4)c(cccc5)c5c4-c4c(cccc5)c5c(-c5ccccc5)c5c4cccc5)c3ccc2)c2)c2c(-c2ccccc2)c2c1cccc2)c1)ccc1-[n]1c(cccc2)c2c2c1cccc2 CLANWCJTTFZQFF-UHFFFAOYSA-N 0.000 description 1
- DDWHELDHRQOAFU-UHFFFAOYSA-N FC(c(cc1)cc(-c2c(cccc3)c3c(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c3c2cccc3)c1F)(F)F Chemical compound FC(c(cc1)cc(-c2c(cccc3)c3c(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c3c2cccc3)c1F)(F)F DDWHELDHRQOAFU-UHFFFAOYSA-N 0.000 description 1
- BQQOLUSAFKCZRH-UHFFFAOYSA-N Fc(c(F)c1)ccc1-c1c(cccc2)c2c(-c(cc2)ccc2-[n]2c(cccc3)c3c3c2cccc3)c2c1cccc2 Chemical compound Fc(c(F)c1)ccc1-c1c(cccc2)c2c(-c(cc2)ccc2-[n]2c(cccc3)c3c3c2cccc3)c2c1cccc2 BQQOLUSAFKCZRH-UHFFFAOYSA-N 0.000 description 1
- OFMKGRGDFVBOEO-UHFFFAOYSA-N Fc(cc1-c2c(cccc3)c3c(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c3c2cccc3)ccc1F Chemical compound Fc(cc1-c2c(cccc3)c3c(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c3c2cccc3)ccc1F OFMKGRGDFVBOEO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本發明關於一種用於合成蒽衍生物之方法。本發明亦關於一種蒽衍生物。本發明進一步關於電流激發發光元件及分別具有此發光元件之發光裝置與電子裝置。 The present invention relates to a method for synthesizing an anthracene derivative. The invention also relates to an anthracene derivative. The invention further relates to a current-excited light-emitting element and a light-emitting device and an electronic device each having the same.
在最近幾年,已廣泛地進行使用電致發光之發光元件的研究及發展。其中具有發光性質之物質被插入一對電極之間的結構被用作該等發光元件之基本結構。來自具有發光性質之物質的發光可藉由施予電壓於該元件而獲得。 In recent years, research and development of light-emitting elements using electroluminescence have been widely conducted. A structure in which a substance having a light-emitting property is inserted between a pair of electrodes is used as a basic structure of the light-emitting elements. Luminescence from a substance having luminescent properties can be obtained by applying a voltage to the element.
因為該發光元件為自發光元件,所以具有如像素之可見度比液晶顯示器之可見度更高且不需要背光的優點。因此,該發光元件被認為適合作為平面顯示器元件。另外,該發光元件可被製成薄且輕,其為一項大的優點。而且,發光元件具有反應速度極快的特點。 Since the light-emitting element is a self-luminous element, there is an advantage that the visibility of the pixel is higher than that of the liquid crystal display and the backlight is not required. Therefore, the light-emitting element is considered to be suitable as a flat display element. In addition, the light-emitting element can be made thin and light, which is a big advantage. Moreover, the light-emitting element has a characteristic that the reaction speed is extremely fast.
此外,因為該等發光元件可形成薄膜形式,所以平面發光可藉由形成大面積元件而輕易地獲得。該特性難以由以白熾燈或LED為代表的點光源,或以螢光燈為代表的 線光源獲得。因此,發光元件具有作為可被施予照明或類似物之平面光源的高利用價值。 Furthermore, since the light-emitting elements can be formed in the form of a film, planar light emission can be easily obtained by forming a large-area element. This feature is difficult to be represented by a point source represented by an incandescent lamp or LED, or by a fluorescent lamp. Line source is obtained. Therefore, the light-emitting element has high utility as a planar light source to which illumination or the like can be applied.
使用電致發光之發光元件係根據彼等是否使用有機化合物或無機化合物作為具有發光性質之物質而被大概分類。 Light-emitting elements using electroluminescence are roughly classified according to whether or not they use an organic compound or an inorganic compound as a substance having luminescent properties.
在具有發光性質之物質為有機化合物的例子中,電子及電洞係藉由施予電壓於發光元件而從一對電極注射至含有具有發光性質之有機化合物的層中,引起電流流動。接著具有發光性質之有機化合物藉由該等載子(電極及電洞)的重組而得到激發態,並在激發態回到基態時發光。因為該機制,所以該種類的發光元件被稱為電流激發類型之發光元件。 In the case where the substance having the luminescent property is an organic compound, electrons and holes are caused to flow in a layer from a pair of electrodes to a layer containing an organic compound having luminescent properties by applying a voltage to the light-emitting element. Then, the organic compound having luminescent properties is excited by the recombination of the carriers (electrodes and holes), and emits light when the excited state returns to the ground state. Because of this mechanism, this type of light-emitting element is called a current-excited type of light-emitting element.
應注意以有機化合物所形成的激發態可為單重激發態或三重激發態。來自單重激發態之發光被稱為螢光,而來自三重激發態之發光被稱為磷光。 It should be noted that the excited state formed by the organic compound may be a singlet excited state or a triplet excited state. Luminescence from a singlet excited state is referred to as fluorescence, and illumination from a triplet excited state is referred to as phosphorescence.
為了克服由該發光元件之材料所衍生的許多問題及改善其元件特性,故進行元件結構的改善、材料開發等等。 In order to overcome many problems derived from the material of the light-emitting element and to improve the characteristics of the element, improvement of the element structure, material development, and the like are performed.
例如,蒽衍生物被發展為發光元件所使用的材料(參見文獻1:日本公開之專利申請案第2003-238534號)。然而,為了合成在文獻1中所揭示之蒽衍生物,需要進行數個步驟。因此,產量不是有利的,而且需要長時間的合成期。 For example, an anthracene derivative has been developed as a material for a light-emitting element (see Document 1: Japanese Published Patent Application No. 2003-238534). However, in order to synthesize the anthracene derivative disclosed in Document 1, several steps are required. Therefore, the yield is not advantageous and requires a long synthesis period.
有鑑於上述問題,故本發明的目的係提供一種以少數步驟合成蒽衍生物之新穎方法。另一目的係提供一種新穎蒽衍生物。進一步的另一目的係提供分別使用蒽衍生物之發光元件、發光裝置及電子裝置。 In view of the above problems, it is an object of the present invention to provide a novel method for synthesizing an anthracene derivative in a few steps. Another object is to provide a novel anthracene derivative. A still further object is to provide a light-emitting element, a light-emitting device, and an electronic device using an anthracene derivative, respectively.
本發明的一個方面為一種用於合成以通式(1)代表的蒽衍生物之方法,該方法係藉由令在10-位置上具有活性位置之9-芳基蒽衍生物與在芳基上具有活性位置之9-芳基咔唑衍生物使用金屬、金屬化合物或金屬觸媒偶合。 One aspect of the present invention is a process for synthesizing an anthracene derivative represented by the formula (1) by reacting a 9-arylindole derivative having an active position at a 10-position with an aryl group The 9-arylcarbazole derivative having an active position thereon is coupled using a metal, a metal compound or a metal catalyst.
在通式(1)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;Ar1代表具有6至25個碳原子之芳基;Ar2代表具有6至25個碳原子之伸芳基;及每一個A1及A2代表氫、具有6至25個碳原子之芳基或具有1至4個碳原子之烷基。 In the formula (1), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; and Ar 1 represents 6 to 25 carbon atoms. Aryl; Ar 2 represents an extended aryl group having 6 to 25 carbon atoms; and each of A 1 and A 2 represents hydrogen, an aryl group having 6 to 25 carbon atoms or an alkane having 1 to 4 carbon atoms base.
本發明的另一方面為一種用於合成以通式(1)代表的蒽衍生物之方法,該方法係藉由令以通式(2)代表的蒽衍生物與以通式(3)代表的咔唑衍生物使用金屬、金屬化合物或金屬觸媒偶合。 Another aspect of the present invention is a process for synthesizing an anthracene derivative represented by the formula (1) by substituting an anthracene derivative represented by the formula (2) with a formula (3) The carbazole derivative is coupled using a metal, a metal compound or a metal catalyst.
在上述合成法中,可提供銅、鐵或類似物作為金屬。可提供碘化銅或類似物作為金屬化合物。可提供鈀觸媒、鎳觸媒或類似物作為金屬觸媒。 In the above synthesis, copper, iron or the like can be provided as the metal. Copper iodide or the like can be provided as the metal compound. A palladium catalyst, a nickel catalyst or the like can be provided as a metal catalyst.
在上述合成法中,硼酸或有機硼較佳地與鹵素在活性位置上偶合。換言之,較佳的是活性位置之一為硼酸或有機硼,而其他為鹵素。當硼酸或有機硼與鹵素在活性位置上偶合時,可獲得高產量的蒽衍生物,此為本發明之一標的。 In the above synthesis, boric acid or organoboron is preferably coupled to the halogen at the active site. In other words, it is preferred that one of the active sites is boric acid or organic boron, and the others are halogen. When boric acid or organoboron is coupled to the halogen at the active site, a high yield of anthracene derivatives can be obtained, which is one of the objects of the present invention.
本發明的另一方面為一種用於合成以通式(1)代表的蒽衍生物之方法,該方法係藉由令9-芳基-10-蒽鹵化物與(咔唑-9-基)芳基硼酸使用金屬觸媒偶合。 Another aspect of the present invention is a process for synthesizing an anthracene derivative represented by the formula (1) by subjecting a 9-aryl-10-hydrazine halide to (carbazol-9-yl) The aryl boronic acid is coupled using a metal catalyst.
在通式(1)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;Ar1代表具有6至25個碳原子之芳基;Ar2代表具有6至25個碳原子之伸芳基;及每一個A1及A2代表氫、具有6至25個碳原子之芳基或具有1至4個碳原子之烷基。 In the formula (1), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; and Ar 1 represents 6 to 25 carbon atoms. Aryl; Ar 2 represents an extended aryl group having 6 to 25 carbon atoms; and each of A 1 and A 2 represents hydrogen, an aryl group having 6 to 25 carbon atoms or an alkane having 1 to 4 carbon atoms base.
在上述合成法中,金屬觸媒較佳為鈀觸媒。 In the above synthesis method, the metal catalyst is preferably a palladium catalyst.
本發明的一個方面為以結構式(12)代表的蒽衍生物。 One aspect of the invention is an anthracene derivative represented by structural formula (12).
本發明的另一方面為以結構式(20)代表的蒽衍生物。 Another aspect of the invention is an anthracene derivative represented by structural formula (20).
本發明的另一方面為以結構式(43)代表的蒽衍生物。 Another aspect of the invention is an anthracene derivative represented by the formula (43).
本發明的另一方面為以結構式(16)代表的蒽衍生物。 Another aspect of the invention is an anthracene derivative represented by the structural formula (16).
本發明的一個方面為一種使用上述蒽衍生物之發光元件。尤其,發光元件具有介於一對電極之間的上述蒽衍生物。 One aspect of the invention is a light-emitting element using the above-described anthracene derivative. In particular, the light-emitting element has the above-described anthracene derivative interposed between a pair of electrodes.
本發明的另一方面為一種具有介於一對電極之間的發光層之發光元件,而該發光層具有上述蒽衍生物。特別 地,上述蒽衍生物較佳地被用作發光物質。換言之,發光元件較佳地具有其中上述蒽衍生物發光之結構。 Another aspect of the present invention is a light-emitting element having a light-emitting layer interposed between a pair of electrodes, and the light-emitting layer has the above-described anthracene derivative. particular The above anthracene derivative is preferably used as a light-emitting substance. In other words, the light-emitting element preferably has a structure in which the above-described anthracene derivative emits light.
本發明的特點在於發光裝置具有含有上述蒽衍生物之發光元件及用於控制發光元件發光之控制器。在本說明書中的發光裝置包括影像顯示裝置、發光裝置及光源(包括照明裝置)。再者,發光裝置亦包括其中有如FPC(軟性印刷電路板)、TAB(捲帶式自動接合)捲帶或TCP(捲帶式載體封裝)之連接器連接於平板的模式;其中印刷線路板係提供在TAP捲帶或TCP末端的模式;及其中IC(積體電路)以COG(覆晶玻璃)法直接架設在發光裝置上的模式。 The present invention is characterized in that the light-emitting device has a light-emitting element including the above-described anthracene derivative and a controller for controlling the light-emitting element to emit light. The light-emitting device in this specification includes an image display device, a light-emitting device, and a light source (including a lighting device). Furthermore, the illuminating device also includes a mode in which a connector such as an FPC (Flexible Printed Circuit Board), a TAB (Tape-Rolled Automatic Coupling) tape or a TCP (tape-type carrier package) is connected to the flat plate; wherein the printed wiring board is A mode provided at the end of the TAP tape or TCP; and a mode in which the IC (integrated circuit) is directly mounted on the light-emitting device by a COG (Flosion-Crystalline) method.
再者,使用本發明的發光元件於顯示部位的電子裝置亦包括在本發明的範疇內。因此,本發明的電子裝置具有顯示部位,而該顯示部位俱備上述發光元件及用於控制發光元件發光之控制器。 Further, an electronic device using the light-emitting element of the present invention at a display portion is also included in the scope of the present invention. Therefore, the electronic device of the present invention has a display portion, and the display portion is provided with the above-described light-emitting element and a controller for controlling the light-emitting element to emit light.
根據本發明,有可能省略用於獲得成為標的的蒽衍生物之合成步驟,並接著有可能比慣例更輕易合成蒽衍生物。另外,反應所需要的時間可以縮短,其導致成本減低。再者,根據本發明,蒽衍生物可以比慣例更高的產量被合成出。 According to the present invention, it is possible to omit the synthetic step for obtaining the target hydrazine derivative, and then it is possible to synthesize the hydrazine derivative more easily than usual. In addition, the time required for the reaction can be shortened, which leads to cost reduction. Further, according to the present invention, an anthracene derivative can be synthesized in a higher yield than conventionally.
具有較大的帶間隙之本發明的蒽衍生物可發出具有短波長的光。再者,此蒽衍生物可發出具有高色彩純度的藍光。 The anthracene derivative of the present invention having a large band gap can emit light having a short wavelength. Further, the anthracene derivative can emit blue light having a high color purity.
使用本發明的蒽衍生物之發光元件可發出具有短波長 的光及具有高色彩純度的藍光。 A light-emitting element using the anthracene derivative of the present invention can emit a short wavelength Light and blue light with high color purity.
再者,具有比本發明的蒽衍生物更小的帶間隙之發光材料(以下被稱為摻雜物)被加入含有本發明的蒽衍生物之層中,藉此可自摻雜物獲得光。此時,因為本發明的蒽衍生物具有極大的帶間隙,所以可有效地獲得不是來自本發明的蒽衍生物,但是來自摻雜物的光,即使使用發出具有相對短波長的光之摻雜物時。尤其,藉由使用具有最大約450奈米波長之發光及顯示極佳的藍色純度之發光材料作為摻雜物,可獲得具有高色彩純度的藍光之發光元件。 Further, a light-emitting material (hereinafter referred to as a dopant) having a smaller gap than the anthracene derivative of the present invention is added to a layer containing the anthracene derivative of the present invention, whereby light can be obtained from the dopant. . At this time, since the anthracene derivative of the present invention has an extremely large band gap, the anthracene derivative which is not derived from the present invention can be efficiently obtained, but the light from the dopant is doped even if light which emits light having a relatively short wavelength is used. When things are. In particular, by using a luminescent material having a wavelength of up to about 450 nm and exhibiting excellent blue purity as a dopant, a blue light-emitting element having high color purity can be obtained.
當製造發光元件時,其中本發明的蒽衍生物被加入含有具有帶間隙比蒽衍生物更大的材料(以下被稱為宿主)之層中,可獲得來自本發明的蒽衍生物之光。換言之,本發明的蒽衍生物充當摻雜物。此時,因為蒽衍生物具有極大的帶間隙及展現具有短波長的光,所以可製造出可獲得具有高色彩純度的藍光之發光元件。 When a light-emitting element is produced in which the anthracene derivative of the present invention is added to a layer containing a material having a larger gap than the anthracene derivative (hereinafter referred to as a host), light derived from the anthracene derivative of the present invention can be obtained. In other words, the anthracene derivative of the present invention acts as a dopant. At this time, since the anthracene derivative has a large band gap and exhibits light having a short wavelength, a light-emitting element which can obtain blue light having high color purity can be manufactured.
當使用含有蒽衍生物之本發明的發光材料時,可獲得提供藍光形式之極佳的色彩純度之發光材料。再者,當使用含有蒽衍生物之本發明的發光材料時,可獲得高可靠度的發光元件。 When a luminescent material of the present invention containing an anthracene derivative is used, a luminescent material which provides excellent color purity in the form of blue light can be obtained. Further, when the luminescent material of the present invention containing an anthracene derivative is used, a highly reliable light-emitting element can be obtained.
含有上述蒽衍生物之本發明的發光元件為可提供藍光形式之極佳的色彩純度的發光元件。再者,含有上述蒽衍生物之本發明的發光元件為高可靠度的發光元件。 The light-emitting element of the present invention containing the above anthracene derivative is a light-emitting element which can provide excellent color purity in a blue light form. Further, the light-emitting element of the present invention containing the above anthracene derivative is a highly reliable light-emitting element.
含有發光元件之本發明的發光裝置為具有高色彩再現性之發光裝置。再者,含有發光元件之本發明的發光裝置 為高可靠度的發光裝置。 The light-emitting device of the present invention containing a light-emitting element is a light-emitting device having high color reproducibility. Furthermore, the light-emitting device of the invention containing the light-emitting element It is a highly reliable light-emitting device.
含有發光元件之本發明的電子裝置為具有高色彩再現性之電子裝置。再者,含有發光元件之本發明的電子裝置為高可靠度的電子裝置。 The electronic device of the present invention containing a light-emitting element is an electronic device having high color reproducibility. Furthermore, the electronic device of the present invention containing a light-emitting element is a highly reliable electronic device.
101‧‧‧基板 101‧‧‧Substrate
102‧‧‧第一個電極 102‧‧‧first electrode
103‧‧‧第一層 103‧‧‧ first floor
104‧‧‧第二層 104‧‧‧ second floor
105‧‧‧第三層 105‧‧‧ third floor
106‧‧‧第四層 106‧‧‧ fourth floor
107‧‧‧第二個電極 107‧‧‧Second electrode
301‧‧‧基板 301‧‧‧Substrate
302‧‧‧第一個電極 302‧‧‧first electrode
303‧‧‧第一層 303‧‧‧ first floor
304‧‧‧第二層 304‧‧‧ second floor
305‧‧‧第三層 305‧‧‧ third floor
306‧‧‧第四層 306‧‧‧ fourth floor
307‧‧‧第二個電極 307‧‧‧Second electrode
501‧‧‧第一個電極 501‧‧‧first electrode
502‧‧‧第二個電極 502‧‧‧Second electrode
511‧‧‧第一個發光單元 511‧‧‧first lighting unit
512‧‧‧第二個發光單元 512‧‧‧Second lighting unit
513‧‧‧電荷產生層 513‧‧‧ Charge generation layer
601‧‧‧源驅動電路 601‧‧‧ source drive circuit
602‧‧‧像素部位 602‧‧‧Pixel parts
603‧‧‧閘驅動電路 603‧‧‧ brake drive circuit
604‧‧‧密封基板 604‧‧‧Seal substrate
605‧‧‧密封材料 605‧‧‧ sealing material
607‧‧‧空間 607‧‧‧ Space
608‧‧‧線路 608‧‧‧ lines
609‧‧‧軟性印刷電路板 609‧‧‧Soft printed circuit board
610‧‧‧元件基板 610‧‧‧ element substrate
611‧‧‧開關TFT 611‧‧‧Switching TFT
612‧‧‧電流控制 612‧‧‧ Current control
613‧‧‧第一個電極 613‧‧‧ first electrode
614‧‧‧絕緣體 614‧‧‧Insulator
616‧‧‧EL層 616‧‧‧EL layer
617‧‧‧第二個電極 617‧‧‧Second electrode
618‧‧‧發光元件 618‧‧‧Lighting elements
623‧‧‧n-通道TFT 623‧‧‧n-channel TFT
624‧‧‧p-通道TFT 624‧‧‧p-channel TFT
901‧‧‧框架 901‧‧‧Frame
902‧‧‧液晶層 902‧‧‧Liquid layer
903‧‧‧背光 903‧‧‧ Backlight
904‧‧‧框架 904‧‧‧Frame
905‧‧‧驅動IC 905‧‧‧Drive IC
906‧‧‧終端 906‧‧‧ Terminal
951‧‧‧基板 951‧‧‧Substrate
952‧‧‧電極 952‧‧‧electrode
953‧‧‧絕緣層 953‧‧‧Insulation
954‧‧‧分隔層 954‧‧‧Separation layer
955‧‧‧EL層 955‧‧‧EL layer
956‧‧‧電極 956‧‧‧electrode
2001‧‧‧框架 2001‧‧‧Frame
2002‧‧‧光源 2002‧‧‧Light source
2101‧‧‧玻璃基板 2101‧‧‧ glass substrate
2102‧‧‧第一個電極 2102‧‧‧first electrode
2103‧‧‧含複合材料的層 2103‧‧‧layers containing composite materials
2104‧‧‧電洞傳輸層 2104‧‧‧ hole transport layer
2105‧‧‧發光層 2105‧‧‧Lighting layer
2106‧‧‧電子傳輸層 2106‧‧‧Electronic transport layer
2107‧‧‧電子注射層 2107‧‧‧Electronic injection layer
2108‧‧‧第二個電極 2108‧‧‧Second electrode
3001‧‧‧照明系統 3001‧‧‧Lighting system
3002‧‧‧電視裝置 3002‧‧‧TV installation
9101‧‧‧框架 9101‧‧‧Frame
9102‧‧‧支撐座 9102‧‧‧ Support
9103‧‧‧顯示部位 9103‧‧‧ Display parts
9104‧‧‧喇叭部位 9104‧‧‧ Horn parts
9105‧‧‧視訊輸入終端 9105‧‧‧Video input terminal
9201‧‧‧主體 9201‧‧‧ Subject
9202‧‧‧框架 9202‧‧‧Frame
9203‧‧‧顯示部位 9203‧‧‧ Display parts
9204‧‧‧鍵盤 9204‧‧‧ keyboard
9205‧‧‧外連結口 9205‧‧‧outer joint
9206‧‧‧指向裝置 9206‧‧‧ pointing device
9401‧‧‧主體 9401‧‧‧ Subject
9402‧‧‧框架 9402‧‧‧Frame
9403‧‧‧顯示部位 9403‧‧‧Display parts
9404‧‧‧視訊輸入部位 9404‧‧‧Video input location
9405‧‧‧視訊輸出部位 9405‧‧‧Video output location
9406‧‧‧操作鍵 9406‧‧‧ operation keys
9407‧‧‧外連結口 9407‧‧‧outer joint
9408‧‧‧天線 9408‧‧‧Antenna
9501‧‧‧主體 9501‧‧‧ Subject
9502‧‧‧顯示部位 9502‧‧‧ Display parts
9503‧‧‧框架 9503‧‧‧Frame
9504‧‧‧外連結口 9504‧‧‧Outer joint
9505‧‧‧遠端控制接收部位 9505‧‧‧ Remote control receiving part
9506‧‧‧影像接受部位 9506‧‧‧Image receiving site
9507‧‧‧電池 9507‧‧‧Battery
9508‧‧‧視訊輸入部位 9508‧‧‧Video input location
9509‧‧‧操作鍵 9509‧‧‧ operation keys
9510‧‧‧目鏡部位 9510‧‧‧ eyepiece parts
圖1A至1C為解釋本發明的發光元件之圖示。 1A to 1C are diagrams for explaining a light-emitting element of the present invention.
圖2為解釋本發明的發光元件之圖示。 Fig. 2 is a view for explaining a light-emitting element of the present invention.
圖3為解釋本發明的發光元件之圖示。 Fig. 3 is a view for explaining a light-emitting element of the present invention.
圖4A及4B為解釋本發明的發光裝置之圖示。 4A and 4B are diagrams for explaining a light-emitting device of the present invention.
圖5A及5B為解釋本發明的發光裝置之圖示。 5A and 5B are diagrams for explaining a light-emitting device of the present invention.
圖6A至6D為分別解釋本發明的電子裝置之圖示。 6A to 6D are diagrams respectively explaining an electronic device of the present invention.
圖7為解釋本發明的電子裝置之圖示。 Figure 7 is a diagram for explaining an electronic device of the present invention.
圖8為解釋本發明的照明系統之圖示。 Figure 8 is a diagram for explaining the illumination system of the present invention.
圖9為解釋本發明的照明系統之圖示。 Figure 9 is a diagram for explaining the illumination system of the present invention.
圖10A及10B為分別顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之1H NMR的圖形。 10A and 10B are graphs showing the 1 H NMR of 9-[4-(N-carbazolyl)phenyl]-10-benzoquinone, respectively.
圖11為顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之甲苯溶液的吸收光譜之圖形。 Figure 11 is a graph showing the absorption spectrum of a toluene solution of 9-[4-(N-carbazolyl)phenyl]-10-phenylhydrazine.
圖12為顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之薄膜的吸收光譜之圖形。 Figure 12 is a graph showing the absorption spectrum of a film of 9-[4-(N-carbazolyl)phenyl]-10-benzoquinone.
圖13為顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之甲苯溶液的發射光譜之圖形。 Figure 13 is a graph showing the emission spectrum of a toluene solution of 9-[4-(N-carbazolyl)phenyl]-10-benzoquinone.
圖14為顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之 薄膜的發射光譜之圖形。 Figure 14 is a graph showing 9-[4-(N-carbazolyl)phenyl]-10-benzoquinone The pattern of the emission spectrum of the film.
圖15A及15B為分別顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之1H NMR的圖形。 15A and 15B are graphs showing the 1 H NMR of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene, respectively.
圖16為顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之甲苯溶液的吸收光譜之圖形。 Figure 16 is a graph showing the absorption spectrum of a toluene solution of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene.
圖17為顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之薄膜的吸收光譜之圖形。 Figure 17 is a graph showing the absorption spectrum of a film of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene.
圖18為顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之甲苯溶液的發射光譜之圖形。 Figure 18 is a graph showing the emission spectrum of a toluene solution of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene.
圖19為顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之薄膜的發射光譜之圖形。 Figure 19 is a graph showing the emission spectrum of a film of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene.
圖20A及20B為分別顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之1H NMR的圖形。 20A and 20B are graphs showing the 1 H NMR of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]benzoquinone, respectively.
圖21為顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之甲苯溶液的吸收光譜之圖形。 Figure 21 is a graph showing the absorption spectrum of a toluene solution of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]phenylhydrazine.
圖22為顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之薄膜的吸收光譜之圖形。 Figure 22 is a graph showing the absorption spectrum of a film of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]benzoquinone.
圖23為顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之甲苯溶液的發射光譜之圖形。 Figure 23 is a graph showing the emission spectrum of a toluene solution of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]phenylhydrazine.
圖24為顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之薄膜的發射光譜之圖形。 Figure 24 is a graph showing the emission spectrum of a film of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]benzoquinone.
圖25A及25B為分別顯示9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽之1H NMR的圖形。 25A and 25B are graphs showing the 1 H NMR of 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethylphenyl)fluorene, respectively.
圖26為顯示9-〔4-(咔唑-9-基)苯基〕-10-(4-三 氟甲基苯基)蒽之甲苯溶液的吸收光譜之圖形。 Figure 26 is a graph showing 9-[4-(carbazol-9-yl)phenyl]-10-(4-tri) A graph of the absorption spectrum of a toluene solution of fluoromethylphenyl) hydrazine.
圖27為顯示9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽之薄膜的吸收光譜之圖形。 Figure 27 is a graph showing the absorption spectrum of a film of 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethylphenyl)fluorene.
圖28為顯示9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽之甲苯溶液的發射光譜之圖形。 Figure 28 is a graph showing the emission spectrum of a toluene solution of 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethylphenyl)fluorene.
圖29為顯示9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽之薄膜的發射光譜之圖形。 Figure 29 is a graph showing the emission spectrum of a film of 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethylphenyl)fluorene.
圖30A及30B為分別顯示9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽之1H NMR的圖形。 30A and 30B are graphs showing the 1 H NMR of 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene, respectively.
圖31為顯示9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽之甲苯溶液的吸收光譜之圖形。 Figure 31 is a graph showing the absorption spectrum of a toluene solution of 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene.
圖32為顯示9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽之薄膜的吸收光譜之圖形。 Figure 32 is a graph showing the absorption spectrum of a film of 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene.
圖33為顯示9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽之甲苯溶液的發射光譜之圖形。 Figure 33 is a graph showing the emission spectrum of a toluene solution of 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene.
圖34為顯示9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽之薄膜的發射光譜之圖形。 Figure 34 is a graph showing the emission spectrum of a film of 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene.
圖35為在具體實施例6中所製造之發光元件的電流密度對亮度特性之圖形。 Fig. 35 is a graph showing current density versus luminance characteristics of the light-emitting element manufactured in Concrete Example 6.
圖36為在具體實施例6中所製造之發光元件的電壓對亮度特性之圖形。 Fig. 36 is a graph showing the voltage versus luminance characteristics of the light-emitting element manufactured in the embodiment 6.
圖37為顯示在具體實施例6中所製造之發光元件的亮度對電流效率特性之圖形。 Fig. 37 is a graph showing the luminance versus current efficiency characteristics of the light-emitting element manufactured in Concrete Example 6.
圖38為顯示在具體實施例6中所製造之發光元件的 發射光譜之圖形。 38 is a view showing a light-emitting element manufactured in Embodiment 6. The spectrum of the emission spectrum.
圖39為在具體實施例7中所製造之發光元件的電流密度對亮度特性之圖形。 Fig. 39 is a graph showing the current density versus luminance characteristics of the light-emitting element manufactured in Concrete Example 7.
圖40為在具體實施例7中所製造之發光元件的電壓對亮度特性之圖形。 Fig. 40 is a graph showing the voltage versus luminance characteristics of the light-emitting element manufactured in Concrete Example 7.
圖41為顯示在具體實施例7中所製造之發光元件的亮度對電流效率特性之圖形。 Fig. 41 is a graph showing the luminance versus current efficiency characteristics of the light-emitting element manufactured in Concrete Example 7.
圖42為顯示在具體實施例7中所製造之發光元件的發射光譜之圖形。 Fig. 42 is a graph showing the emission spectrum of the light-emitting element manufactured in Specific Example 7.
圖43為在具體實施例8中所製造之發光元件的電流密度對亮度特性之圖形。 Figure 43 is a graph showing the current density versus luminance characteristics of the light-emitting element manufactured in Concrete Example 8.
圖44為在具體實施例8中所製造之發光元件的電壓對亮度特性之圖形。 Fig. 44 is a graph showing the voltage versus luminance characteristics of the light-emitting element manufactured in the eighth embodiment.
圖45為顯示在具體實施例8中所製造之發光元件的亮度對電流效率特性之圖形。 Fig. 45 is a graph showing the luminance versus current efficiency characteristics of the light-emitting element manufactured in Concrete Example 8.
圖46為顯示在具體實施例8中所製造之發光元件的發射光譜之圖形。 Fig. 46 is a graph showing the emission spectrum of the light-emitting element manufactured in Specific Example 8.
圖47為在具體實施例9中所製造之發光元件的電流密度對亮度特性之圖形。 Figure 47 is a graph showing the current density versus luminance characteristics of the light-emitting element manufactured in Concrete Example 9.
圖48為在具體實施例9中所製造之發光元件的電壓對亮度特性之圖形。 Figure 48 is a graph showing the voltage versus luminance characteristics of the light-emitting element manufactured in Concrete Example 9.
圖49為顯示在具體實施例9中所製造之發光元件的亮度對電流效率特性之圖形。 Fig. 49 is a graph showing the luminance versus current efficiency characteristics of the light-emitting element manufactured in Concrete Example 9.
圖50為顯示在具體實施例9中所製造之發光元件的 發射光譜之圖形。 Figure 50 is a view showing a light-emitting element manufactured in Concrete Example 9. The spectrum of the emission spectrum.
圖51為在具體實施例10中所製造之發光元件的電流密度對亮度特性之圖形。 Figure 51 is a graph showing the current density versus luminance characteristics of the light-emitting element manufactured in Concrete Example 10.
圖52為在具體實施例10中所製造之發光元件的電壓對亮度特性之圖形。 Figure 52 is a graph showing the voltage versus luminance characteristics of the light-emitting element manufactured in Concrete Example 10.
圖53為顯示在具體實施例10中所製造之發光元件的亮度對電流效率特性之圖形。 Figure 53 is a graph showing the luminance versus current efficiency characteristics of the light-emitting element manufactured in Concrete Example 10.
圖54為顯示在具體實施例10中所製造之發光元件的發射光譜之圖形。 Fig. 54 is a graph showing the emission spectrum of the light-emitting element manufactured in Specific Example 10.
圖55為解釋具體實施例的發光元件之圖示。 Figure 55 is a diagram for explaining a light-emitting element of a specific embodiment.
圖56為顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之還原端的CV測量結果之圖形。 Figure 56 is a graph showing the results of CV measurement of the reducing end of 9-[4-(N-carbazolyl)phenyl]-10-phenylhydrazine.
圖57為顯示9-〔4-(N-咔唑基)苯基〕-10-苯蒽之氧化端的CV測量結果之圖形。 Fig. 57 is a graph showing the results of CV measurement of the oxidation end of 9-[4-(N-carbazolyl)phenyl]-10-phenylhydrazine.
圖58為顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之還原端的CV測量結果之圖形。 Figure 58 is a graph showing the results of CV measurement of the reducing end of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene.
圖59為顯示9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽之氧化端的CV測量結果之圖形。 Figure 59 is a graph showing the results of CV measurement of the oxidation end of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]fluorene.
圖60為顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之還原端的CV測量結果之圖形。 Figure 60 is a graph showing the results of CV measurement of the reducing end of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]phenylhydrazine.
圖61為顯示9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽之氧化端的CV測量結果之圖形。 Figure 61 is a graph showing the results of CV measurement of the oxidation end of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]phenylhydrazine.
圖62為顯示9-〔4-(N-咔唑基)苯基〕-10-(4-三氟甲基苯基)蒽之還原端的CV測量結果之圖形。 Fig. 62 is a graph showing the results of CV measurement of the reducing end of 9-[4-(N-carbazolyl)phenyl]-10-(4-trifluoromethylphenyl)fluorene.
圖63為顯示9-〔4-(N-咔唑基)苯基〕-10-(4-三氟甲基苯基)蒽之氧化端的CV測量結果之圖形。 Figure 63 is a graph showing the results of CV measurement of the oxidation end of 9-[4-(N-carbazolyl)phenyl]-10-(4-trifluoromethylphenyl)fluorene.
圖64為顯示9-〔4-(N-咔唑基)苯基〕-10-(2-萘基)蒽之還原端的CV測量結果之圖形。 Fig. 64 is a graph showing the results of CV measurement of the reducing end of 9-[4-(N-carbazolyl)phenyl]-10-(2-naphthyl)anthracene.
圖65為顯示9-〔4-(N-咔唑基)苯基〕-10-(2-萘基)蒽之氧化端的CV測量結果之圖形。 Fig. 65 is a graph showing the results of CV measurement of the oxidation end of 9-[4-(N-carbazolyl)phenyl]-10-(2-naphthyl)anthracene.
於下文,本發明的具體實施例模式以參考所附圖式被詳細地敘述。然而,本發明不限於下列敘述,熟諳本技藝者可輕易瞭解各種變化及修改是可能的,除非該等變化及修改脫離本發明的內容及範圍。因此,不將本發明解釋成被限制於下列具體實施例模式的敘述。 Hereinafter, specific mode modes of the present invention are described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following description, and it is obvious to those skilled in the art that various changes and modifications may be made without departing from the scope and scope of the invention. Therefore, the present invention is not to be construed as being limited to the description of the specific embodiments.
此具體實施例模式敘述一種用於合成本發明的蒽衍生物之方法。 This specific embodiment mode describes a method for synthesizing the anthracene derivative of the present invention.
在用於合成本發明的蒽衍生物之方法中,將在10-位置上具有活性位置之9-芳基蒽衍生物與在芳基上具有活性位置之9-芳基咔唑衍生物使用金屬、金屬化合物或金屬觸媒偶合,得以合成以通式(1)代表的蒽衍生物。 In the method for synthesizing the anthracene derivative of the present invention, a 9-arylindole derivative having an active position at the 10-position and a 9-arylcarbazole derivative having an active position on the aryl group are used as a metal. The metal compound or the metal catalyst is coupled to synthesize the anthracene derivative represented by the formula (1).
更尤其將在9-位置上具有芳基Ar1及在10-位置上具有活性位置之9-芳基蒽衍生物與在9-位置上具有芳基Ar2 及在芳基Ar2上具有活性位置之9-芳基咔唑衍生物使用金屬、金屬化合物或金屬觸媒偶合,得以合成以通式(1)代表的蒽衍生物。 More particularly, it will have an aryl group Ar 1 at the 9-position and a 9-aryl fluorene derivative having an active position at the 10-position, and have an aryl group Ar 2 at the 9-position and be active on the aryl group Ar 2 . The 9-arylcarbazole derivative at a position is coupled with a metal, a metal compound or a metal catalyst to synthesize an anthracene derivative represented by the formula (1).
換言之,將以通式(2)代表的蒽衍生物與以通式(3)代表的咔唑衍生物使用金屬、金屬化合物或金屬觸媒偶合,可得以合成以通式(1)代表的蒽衍生物。 In other words, by coupling a hydrazine derivative represented by the general formula (2) with a carbazole derivative represented by the general formula (3) using a metal, a metal compound or a metal catalyst, a hydrazine represented by the general formula (1) can be synthesized. derivative.
在通式(1)至(3)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;Ar1代表具有6至25個碳原子之芳基;Ar2代表具有6至25個碳原子之伸芳基;及每一個A1及A2代表氫、具有6至25個碳原子之芳基或具有1至4個碳原子之烷基。每一個Ar1、Ar2、A1及A2可具有取代基。可提供具有1至4個碳原子之烷基、具有6至25個碳原子之芳基、鹵素、鹵烷基、氰基、硝基、酯基、烷氧基羰基、醯氧基、烷氧基、醯基、甲醯基、羥基或類似物作為取代基。尤其可提下列者:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、苯基、鄰-甲苯基、間-甲苯基、對-甲苯基、1-萘基、2-萘基、鄰-聯苯基、間-聯苯基、對-聯苯基、對-聯三苯-4-基、對-聯三苯-3-基、對-聯三苯-2-基、間-聯三苯-4-基、間-聯三苯-3-基、間-聯三苯-2-基、鄰-聯三苯-4-基、鄰-聯三苯-3-基、鄰-聯三苯-2-基、茀-2-基、9,9-二甲基茀-2-基、9,9-二苯基茀-2-基、螺旋-9,9’-二茀-2-基、氟、氯、溴、碘、三氟 甲基、氰基、硝基、甲酯基、乙酯基、甲氧基羰基、乙氧基羰基、乙醯氧基、甲氧基、乙氧基、羧基、乙醯基、醛基或羥基。 In the general formulae (1) to (3), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; and Ar 1 represents having 6 to Aryl group of 25 carbon atoms; Ar 2 represents an extended aryl group having 6 to 25 carbon atoms; and each of A 1 and A 2 represents hydrogen, an aryl group having 6 to 25 carbon atoms or has 1 to 4 An alkyl group of carbon atoms. Each of Ar 1 , Ar 2 , A 1 and A 2 may have a substituent. An alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 25 carbon atoms, a halogen, a haloalkyl group, a cyano group, a nitro group, an ester group, an alkoxycarbonyl group, a decyloxy group, an alkoxy group can be provided. A group, a mercapto group, a decyl group, a hydroxyl group or the like is used as a substituent. In particular, the following may be mentioned: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, phenyl, o-tolyl, m-tolyl , p-tolyl, 1-naphthyl, 2-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, p-terphenyl-4-yl, p-terphenyl 3-yl, p-bitriphenyl-2-yl, m-triphenyl-4-yl, m-triphenyl-3-yl, m-triphenyl-2-yl, o-triphenyl- 4-yl, o-terphenyl-3-yl, o-triphenyl-2-yl, indol-2-yl, 9,9-dimethylinden-2-yl, 9,9-diphenyl Indole-2-yl, helix-9,9'-diin-2-yl, fluoro, chloro, bromo, iodo, trifluoromethyl, cyano, nitro, methyl, ethyl, methoxy Carbonyl, ethoxycarbonyl, ethoxylated, methoxy, ethoxy, carboxyl, ethyl, aldehyde or hydroxy.
再者,可提供鹵素、硼酸、有機硼、有機錫、三氟甲烷磺酸酯、Grignard試劑、有機汞、硫代氰酸酯、有機鋅、有機鋁、有機鋯或類似物於每一活性位置X3及活性位置X6。 Further, halogen, boric acid, organoboron, organotin, trifluoromethanesulfonate, Grignard reagent, organic mercury, thiocyanate, organozinc, organoaluminum, organozirconium or the like may be provided at each active site. X 3 and active position X 6 .
可提供如銅或鐵之金屬、如碘化亞銅(I)之金屬化合物、如鈀觸媒或鎳觸媒之金屬觸媒作為用於反應的金屬、金屬化合物或金屬觸媒。 A metal such as copper or iron, a metal compound such as copper (I) iodide, a metal catalyst such as a palladium catalyst or a nickel catalyst may be provided as a metal, a metal compound or a metal catalyst for the reaction.
一種用於合成本發明的蒽衍生物之方法被詳細敘述於下。藉由合成本發明的蒽衍生物之方法,使具有活性位置X3之9-芳基蒽衍生物(化合物E)與具有活性位置X6之9-芳基咔唑衍生物(化合物H)在使用如銅或鐵之金屬或如碘化亞銅(I)之金屬化合物下進行偶合反應,如合成流程(A-4)所示,可得以合成蒽衍生物(化合物I),此為標的物。金屬或金屬化合物可為金屬觸媒,如鈀觸媒或鎳觸媒。可使用Suzuki-Miyaura偶合、Migita-Kosugi-Stille偶合、Kumada-Tamao偶合、Negishi偶合或類似反應作為偶合反應。 A method for synthesizing the anthracene derivative of the present invention is described in detail below. Anthracene derivative synthesized by the method of the present invention, X 3 makes it the 9-arylanthracene derivative (compound E) having an active position and an active position X 6 aryl group of the carbazole derivative 9- (Compound H) in The coupling reaction can be carried out by using a metal such as copper or iron or a metal compound such as copper (I) iodide, as shown in the synthetic scheme (A-4), which is a target compound. . The metal or metal compound may be a metal catalyst such as a palladium catalyst or a nickel catalyst. A Suzuki-Miyaura coupling, a Migita-Kosugi-Stille coupling, a Kumada-Tamao coupling, a Negishi coupling or the like can be used as the coupling reaction.
具有活性位置X3之9-芳基蒽衍生物(化合物E)可以下述方法合成。首先,如合成流程(A-1)所示,蒽衍生物(化合物A)(在9-位置上的碳,為活性的,例如9-蒽鹵化物)與具有反應活性碳之芳烴(化合物B)(如芳基硼酸)係在使用如銅或鐵之金屬、如碘化亞銅(I)之金屬化合物、如鈀觸媒或鎳觸媒之金屬觸媒下進行偶合反應,得以獲得9-芳基蒽衍生物(化合物C)。 The 9-arylindole derivative (Compound E) having an active position X 3 can be synthesized by the following method. First, as shown in the synthetic scheme (A-1), an anthracene derivative (Compound A) (carbon at the 9-position, which is active, such as 9-fluorene halide) and an aromatic hydrocarbon having a reactive carbon (Compound B) (e.g., arylboronic acid) is obtained by coupling reaction using a metal such as copper or iron, a metal compound such as copper (I) iodide, or a metal catalyst such as a palladium catalyst or a nickel catalyst. Aryl hydrazine derivative (Compound C).
接著,如合成流程(A-2)所示,在10-位置上的碳被活化(如9-芳基蒽衍生物(化合物C)的鹵化作用),可得以獲得具有活性位置X3之9-芳基蒽衍生物(化合物E)。 Next, as shown in the synthesis scheme (A-2), carbon at the 10-position is activated (for example, halogenation of a 9-aryl hydrazine derivative (compound C)), and 9 having an active position X 3 can be obtained. - an aryl hydrazine derivative (Compound E).
在其中具有活性位置X3之9-芳基蒽衍生物(化合物E)為9-芳基-10-蒽鹵化物或9-芳基-10-三氟甲烷磺酸蒽的例子中,合成可藉由合成流程(A-3)所示之方法進行。尤其,其中在9-位置上的碳及在10-位置上的碳被活化之蒽衍生物(化合物F)與具有反應活性碳芳烴(化合物G)(如芳基硼酸)使用如銅或鐵之金屬、如碘化亞銅(I)金屬化合物、如鈀觸媒或鎳觸媒之金屬觸媒偶合,可得以獲得具有活性位置X3之9-芳基蒽衍生物(化合物E)。 In the case where the 9-arylindole derivative (compound E) having an active position X 3 is 9-aryl-10-hydrazine halide or 9-aryl-10-trifluoromethanesulfonate oxime, the synthesis can be This is carried out by the method shown in the synthesis scheme (A-3). In particular, the carbon in the 9-position and the carbon-activated anthracene derivative (compound F) at the 10-position and the reactive carbon-aromatic (compound G) (such as arylboronic acid) are used, such as copper or iron. The metal-catalyzed coupling of a metal such as a copper (I) iodide metal compound such as a palladium catalyst or a nickel catalyst can obtain a 9-arylindole derivative (compound E) having an active position X 3 .
在上述流程(A-1)至(A-4)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;Ar1代表具有6至25個碳原子之芳基;Ar2代表具有6至25個碳原子之伸芳基;及每一個A1及A2代表氫、具有6至25個碳原子之芳基或具有1至4個碳原 子之烷基。每一個Ar1、Ar2、A1及A2可具有取代基。取代基可為具有1至4個碳原子之烷基、具有6至25個碳原子之芳基、鹵素、鹵烷基、氰基、硝基、羰基、酯基、烷氧基或類似物。 In the above schemes (A-1) to (A-4), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; Ar 1 Represents an aryl group having 6 to 25 carbon atoms; Ar 2 represents an extended aryl group having 6 to 25 carbon atoms; and each of A 1 and A 2 represents hydrogen, an aryl group having 6 to 25 carbon atoms or has An alkyl group of 1 to 4 carbon atoms. Each of Ar 1 , Ar 2 , A 1 and A 2 may have a substituent. The substituent may be an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 25 carbon atoms, a halogen, a haloalkyl group, a cyano group, a nitro group, a carbonyl group, an ester group, an alkoxy group or the like.
在上述流程(A-1)至(A-4)中,每一個X1至X6代表鹵素、硼酸、有機硼、有機錫、三氟甲烷磺酸酯、Grignard試劑、有機汞、硫代氰酸酯、有機鋅、有機鋁或有機鋯。 In the above schemes (A-1) to (A-4), each of X 1 to X 6 represents halogen, boric acid, organoboron, organotin, trifluoromethanesulfonate, Grignard reagent, organic mercury, thiocyanate Acid ester, organozinc, organoaluminum or organozirconium.
每一合成流程被詳細地敘述於下。特別敘述反應活性位置(X1至X6)的特殊組合。首先敘述合成流程(A-4)。當Suzuki-Miyaura偶合用於具有活性位置X3之9-芳基蒽衍生物(化合物E)與具有活性位置X6之9-芳基咔唑(化合物H)的偶合反應時,如合成流程(A-4)所代表,則較佳的是X3為鹵素或三氟甲烷磺酸酯及X6為硼酸或有機硼。或者,較佳的是X3為硼酸或有機硼及X6為鹵素或三氟甲烷磺酸酯。而且,較佳地使用鈀觸媒。當X3及X6為鹵素時,則以溴或碘較佳,換言之,以合成流程(A-14a)或合成流程(A-14b)所示之合成方法較佳。 Each synthesis process is described in detail below. Particular combinations of reactive sites (X 1 to X 6 ) are specifically described. First, the synthesis scheme (A-4) will be described. When Suzuki-Miyaura coupling active position to X 3 of the 9-arylanthracene derivative (compound E) having an active position when the X 6 9- aryl carbazole (Compound H) in a coupling reaction, such as synthetic scheme ( As represented by A-4), it is preferred that X 3 is halogen or trifluoromethanesulfonate and X 6 is boric acid or organic boron. Alternatively, it is preferred that X 3 is boric acid or organic boron and X 6 is halogen or trifluoromethanesulfonate. Moreover, a palladium catalyst is preferably used. When X 3 and X 6 are halogen, bromine or iodine is preferred, in other words, the synthesis method shown in the synthesis scheme (A-14a) or the synthesis scheme (A-14b) is preferred.
在上述流程(A-14a)及(A-14b)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;Ar1代表具有6至25個碳原子之芳基; Ar2代表具有6至25個碳原子之伸芳基;及每一個A1及A2代表氫、具有6至25個碳原子之芳基或具有1至4個碳原子之烷基。每一個Ar1、Ar2、A1及A2可具有取代基。取代基可為具有1至4個碳原子之烷基、具有6至25個碳原子之芳基、鹵素、鹵烷基、氰基、硝基、羰基、酯基、烷氧基或類似物。X13及X16代表鹵素,而每一個R31及R32代表具有1至6個碳原子之烷基。應注意R31與R32組合形成環。 In the above schemes (A-14a) and (A-14b), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; Ar 1 Represents an aryl group having 6 to 25 carbon atoms; Ar 2 represents an extended aryl group having 6 to 25 carbon atoms; and each of A 1 and A 2 represents hydrogen, an aryl group having 6 to 25 carbon atoms or has An alkyl group of 1 to 4 carbon atoms. Each of Ar 1 , Ar 2 , A 1 and A 2 may have a substituent. The substituent may be an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 25 carbon atoms, a halogen, a haloalkyl group, a cyano group, a nitro group, a carbonyl group, an ester group, an alkoxy group or the like. X 13 and X 16 represent a halogen, and each of R 31 and R 32 represents an alkyl group having 1 to 6 carbon atoms. It should be noted that R 31 and R 32 combine to form a ring.
在具有活性位置X3之9-芳基蒽衍生物(化合物E)與具有活性位置X6之9-芳基咔唑(化合物H)的偶合反應中,如以合成流程(A-4)所代表,可獲得具有極高產率之蒽衍生物(化合物I),此為標的物;因此,較佳地進行Suzuki-Miyaura偶合。 In the coupling reaction of a 9-arylindole derivative (compound E) having an active position X 3 with a 9-arylcarbazole having an active position X 6 (compound H), as in the synthetic scheme (A-4) Representative, an anthracene derivative (Compound I) having a very high yield can be obtained, which is the subject; therefore, Suzuki-Miyaura coupling is preferably carried out.
在具有活性位置X3之9-芳基蒽衍生物(化合物E)與具有活性位置X6之9-芳基咔唑(化合物H)的偶合反應中,如合成流程(A-4)所代表,當X3為鹵素時,則X6為Grignard試劑、有機錫或有機汞。藉由進行使用金屬、金屬化合物或金屬觸媒(如鈀觸媒或鎳觸媒)的偶合反應,可合成蒽衍生物(化合物I)。或者,當X6為鹵素時,則X3為Grignard試劑、有機錫或有機汞。藉由進行使用金屬、金屬化合物或金屬觸媒(如鈀觸媒或鎳觸媒)的偶合反應,可合成蒽衍生物(化合物I),此為標的物。 In the coupling reaction of a 9-arylindole derivative (compound E) having an active position X 3 with a 9-arylcarbazole having an active position X 6 (compound H), as represented by the synthetic scheme (A-4) When X 3 is a halogen, then X 6 is a Grignard reagent, organotin or organic mercury. The anthracene derivative (compound I) can be synthesized by performing a coupling reaction using a metal, a metal compound or a metal catalyst such as a palladium catalyst or a nickel catalyst. Alternatively, when X 6 is a halogen, then X 3 is a Grignard reagent, organotin or organic mercury. The indole derivative (compound I) can be synthesized by carrying out a coupling reaction using a metal, a metal compound or a metal catalyst such as a palladium catalyst or a nickel catalyst, which is the subject matter.
在具有活性位置X3之9-芳基蒽衍生物(化合物E) 與具有活性位置X6之9-芳基咔唑(化合物H)的偶合反應中,當X3及X6為鹵素或硫代氰酸酯時,則蒽衍生物(化合物I)(其為標的物)可藉由其中使用銅或銅化合物之Ullmann反應而合成。在其中進行Ullmann反應的例子中,雖然X3及X6可彼此相同或不同,但是X3及X6較佳為碘。 In the coupling reaction of a 9-arylindole derivative (compound E) having an active position X 3 with a 9-arylcarbazole having an active position X 6 (compound H), when X 3 and X 6 are halogen or sulfur In the case of a cyanate ester, the anthracene derivative (Compound I) which is the subject matter can be synthesized by a Ullmann reaction in which a copper or copper compound is used. In the example in which the Ullmann reaction is carried out, although X 3 and X 6 may be the same or different from each other, X 3 and X 6 are preferably iodine.
接著詳細敘述合成流程(A-1)。當在9-芳基蒽衍生物(化合物C)之合成中進行Suzuki-Miyaura偶合時,如合成流程(A-1)所代表,則較佳的是X1為鹵素或三氟甲烷磺酸酯及X2為硼酸或有機硼。例如,較佳地使用9-芳基-10-蒽鹵化物及(咔唑-9-基)芳基硼酸。或者,較佳的是X1為硼酸或有機硼及X2為鹵素或三氟甲烷磺酸酯。再者,較佳地使用鈀觸媒。當X1及X2為鹵素時,則以溴或碘較佳,換言之,合成流程(A-1)較佳為合成流程(A-11a)或合成流程(A-11b)。 Next, the synthesis scheme (A-1) will be described in detail. When Suzuki-Miyaura coupling is carried out in the synthesis of a 9-arylindole derivative (Compound C), as represented by the synthetic scheme (A-1), it is preferred that X 1 is a halogen or a trifluoromethanesulfonate. And X 2 is boric acid or organic boron. For example, 9-aryl-10-hydrazine halide and (carbazol-9-yl)arylboronic acid are preferably used. Alternatively, it is preferred that X 1 is boric acid or organic boron and X 2 is halogen or trifluoromethanesulfonate. Further, a palladium catalyst is preferably used. When X 1 and X 2 are halogen, bromine or iodine is preferred, in other words, the synthesis scheme (A-1) is preferably a synthetic scheme (A-11a) or a synthetic scheme (A-11b).
在上述流程(A-11a)及(A-11b)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;及Ar1代表具有6至25個碳原子之芳基。Ar1可具有取代基。取代基可為具有1至4個碳原子之烷基、具有6至25個碳原子之芳基、鹵素、鹵烷基、氰基、硝基、羰基、酯基、烷氧基或類似物。X11及X12代表鹵素,而每一個R11及R12代表具有1至6個碳原子之烷基。應注意R11與R12組合形成環。 In the above schemes (A-11a) and (A-11b), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; and Ar 1 represents an aryl group having 6 to 25 carbon atoms. Ar 1 may have a substituent. The substituent may be an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 25 carbon atoms, a halogen, a haloalkyl group, a cyano group, a nitro group, a carbonyl group, an ester group, an alkoxy group or the like. X 11 and X 12 represent a halogen, and each of R 11 and R 12 represents an alkyl group having 1 to 6 carbon atoms. It should be noted that R 11 and R 12 combine to form a ring.
在合成流程(A-1)所代表的9-芳基蒽衍生物(化合物C)之合成中,可獲得具有極高產率之9-芳基蒽衍生物(化合物C),其為標的物;因此,較佳地進行Suzuki-Miyaura偶合。特別考慮合成材料的容易性,故較佳的是X1為鹵素或三氟甲烷磺酸酯及X2為硼酸或有機硼。 In the synthesis of the 9-arylindole derivative (Compound C) represented by the synthetic scheme (A-1), a 9-arylindole derivative (Compound C) having a very high yield, which is a target substance, can be obtained; Therefore, Suzuki-Miyaura coupling is preferably carried out. In particular, the ease of the synthetic material is considered, so it is preferred that X 1 is a halogen or a trifluoromethanesulfonate and X 2 is a boric acid or an organic boron.
當X1為鹵素時,則X2為Grignard試劑、有機錫、有機汞、硼酸或有機硼。藉由進行使用金屬、金屬化合物或 金屬觸媒(如鈀觸媒或鎳觸媒)的偶合反應,可合成9-芳基蒽衍生物(化合物C)。或者,當X2為鹵素時,則X1為Grignard試劑、有機錫、有機汞、硼酸或有機硼。藉由進行使用金屬、金屬化合物或金屬觸媒(如鈀觸媒或鎳觸媒)的偶合反應,可合成9-芳基蒽衍生物(化合物C)。 When X 1 is a halogen, then X 2 is a Grignard reagent, organotin, organomercury, boric acid or organoboron. The 9-arylindole derivative (Compound C) can be synthesized by performing a coupling reaction using a metal, a metal compound or a metal catalyst such as a palladium catalyst or a nickel catalyst. Alternatively, when X 2 is a halogen, then X 1 is a Grignard reagent, organotin, organomercury, boric acid or organoboron. The 9-arylindole derivative (Compound C) can be synthesized by performing a coupling reaction using a metal, a metal compound or a metal catalyst such as a palladium catalyst or a nickel catalyst.
當X1及X2為鹵素或硫代氰酸酯時,則蒽衍生物(化合物A)與具有反應活性碳之芳烴(化合物B)藉由使用銅或銅化合物之Ullmann反應而偶合,可得以合成9-芳基蒽衍生物(化合物C)。在其中進行Ullmann反應的例子中,雖然X1及X2可彼此相同或不同,但是X1及X2較佳為碘。 When X 1 and X 2 are halogen or thiocyanate, the anthracene derivative (compound A) and the aromatic hydrocarbon having a reactive carbon (compound B) are coupled by a Ullmann reaction using a copper or copper compound. Synthesis of a 9-arylindole derivative (Compound C). In the example in which the Ullmann reaction is carried out, although X 1 and X 2 may be the same or different from each other, X 1 and X 2 are preferably iodine.
接著詳細敘述合成流程(A-2)。在10-位置上的碳被活化,如以合成流程(A-12)所代表的9-芳基蒽衍生物(化合物C)的鹵化作用,可得以獲得具有活性位置X3之9-芳基蒽衍生物(化合物E)。當在鹵化反應中進行溴化作用時,則溴化作用可使用溴、N-溴基琥珀醯亞胺(NBS)或類似物進行。或者,當進行碘化作用時,則碘化作用可使用碘、原高碘酸、碘化鉀、N-碘基琥珀醯亞胺或類似物進行。 Next, the synthesis scheme (A-2) will be described in detail. The carbon at the 10-position is activated, such as the halogenation of the 9-arylindole derivative (compound C) represented by the synthetic scheme (A-12), and the 9-aryl group having the active position X 3 can be obtained. Anthracene derivative (Compound E). When bromination is carried out in the halogenation reaction, bromination can be carried out using bromine, N-bromosuccinimide (NBS) or the like. Alternatively, when iodination is carried out, iodination can be carried out using iodine, properiodate, potassium iodide, N-iodosuccinimide or the like.
接著詳細敘述合成流程(A-3)。當在合成流程(A- 3)所代表的反應中進行Suzuki-Miyaura偶合時,則較佳的是X4為鹵素或三氟甲烷磺酸酯及X5為硼酸或有機硼。 或者,較佳的是X4為硼酸或有機硼及X5為鹵素或三氟甲烷磺酸酯。再者,較佳地使用鈀觸媒。當X4及X5為鹵素時,則以溴或碘較佳。 Next, the synthesis scheme (A-3) will be described in detail. When Suzuki-Miyaura coupling is carried out in the reaction represented by the synthesis scheme (A-3), it is preferred that X 4 is halogen or trifluoromethanesulfonate and X 5 is boric acid or organic boron. Alternatively, it is preferred that X 4 is boric acid or organic boron and X 5 is halogen or trifluoromethanesulfonate. Further, a palladium catalyst is preferably used. When X 4 and X 5 are halogen, bromine or iodine is preferred.
換言之,當具有活性位置X3之芳基蒽衍生物(化合物E)為在10-位置上具有三氟甲烷磺酸酯基團作為反應活性位置的9-芳基-10-蒽鹵化物或9-蒽時,則9,10-二鹵化蒽(化合物F)及芳基硼酸(化合物G)可藉由使用鈀觸媒或類似物以1:1之莫耳比進行偶合反應而合成,如合成流程(A-13a)所代表。同時,芳基硼酸(化合物G)可為芳基有機硼化合物。或者,蒽-9,10-二硼酸(化合物F)及鹵化芳烴(化合物G)使用鈀觸媒或類似物以1:1之莫耳比進行偶合反應,如合成流程(A-13b)所代表,可合成9-芳基-10-蒽鹵化物。同時,蒽-9,10-二硼酸(化合物F)可為蒽-9,10-雙有機硼化合物。 In other words, when the aryl hydrazine derivative (compound E) having the active position X 3 is a 9-aryl-10-hydrazine halide having a trifluoromethanesulfonate group at the 10-position as a reactive site or 9 - in the case of ruthenium, 9,10-dihalogenated ruthenium (compound F) and arylboronic acid (compound G) can be synthesized by a coupling reaction using a palladium catalyst or the like at a molar ratio of 1:1, such as synthesis. Represented by process (A-13a). Meanwhile, the arylboronic acid (Compound G) may be an aryl organoboron compound. Alternatively, hydrazine-9,10-diboronic acid (compound F) and a halogenated aromatic hydrocarbon (compound G) are coupled using a palladium catalyst or the like at a molar ratio of 1:1, as represented by the synthetic scheme (A-13b). , 9-aryl-10-oxime halide can be synthesized. Meanwhile, -9,10-diboronic acid (Compound F) may be a ruthenium-9,10-diorgano boron compound.
在上述流程(A-13a)及(A-13b)中,每一個R1至R8代表氫、具有1至4個碳原子之烷基或具有6至15個碳原子之芳基;及Ar1代表具有6至25個碳原子之芳基。Ar1可具有取代基。取代基可為具有1至4個碳原子之烷基、具有6至25個碳原子之芳基、鹵素、鹵烷基、氰基、硝基、羰基、酯基、烷氧基或類似物。X13、X14及X15代表鹵素,而每一個R21及R22代表具有1至6個碳原子之烷基。應注意R21與R22組合形成環。 In the above schemes (A-13a) and (A-13b), each of R 1 to R 8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 15 carbon atoms; and Ar 1 represents an aryl group having 6 to 25 carbon atoms. Ar 1 may have a substituent. The substituent may be an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 25 carbon atoms, a halogen, a haloalkyl group, a cyano group, a nitro group, a carbonyl group, an ester group, an alkoxy group or the like. X 13 , X 14 and X 15 represent a halogen, and each of R 21 and R 22 represents an alkyl group having 1 to 6 carbon atoms. It should be noted that R 21 and R 22 combine to form a ring.
可藉由令在9-位置上的碳及在10-位置上的碳被活化之蒽衍生物(化合物F)與具有反應活性碳之芳烴(化合物G)進行的偶合反應而獲得具有極高產率之標的物,如合成流程(A-3)所代表;因此,較佳地進行Suzuki-Miyaura偶合。特別考慮合成材料的容易性,故較佳的是X6為鹵素或三氟甲烷磺酸酯及X4為硼酸或有機硼。 Very high yield can be obtained by coupling a carbon at the 9-position and a carbon-activated anthracene derivative (compound F) at the 10-position with an aromatic hydrocarbon (compound G) having a reactive carbon. The subject matter is represented by the synthetic scheme (A-3); therefore, Suzuki-Miyaura coupling is preferably carried out. In particular, the ease of the synthetic material is considered, so it is preferred that X 6 is a halogen or a trifluoromethanesulfonate and X 4 is a boric acid or an organic boron.
當X4為鹵素時,則X5為Grignard試劑、有機錫、有 機汞、硼酸或有機硼。藉由進行使用金屬、金屬化合物或金屬觸媒(如鈀觸媒或鎳觸媒)的偶合反應,可合成9-芳基蒽衍生物(化合物E)。或者,當X5為鹵素時,則X4為Grignard試劑、有機錫、有機汞、硼酸或有機硼。藉由進行使用金屬、金屬化合物或金屬觸媒(如鈀觸媒或鎳觸媒)的偶合反應。可合成9-芳基蒽衍生物(化合物E)。 When X 4 is a halogen, then X 5 is a Grignard reagent, organotin, organomercury, boric acid or organoboron. The 9-arylindole derivative (compound E) can be synthesized by performing a coupling reaction using a metal, a metal compound or a metal catalyst such as a palladium catalyst or a nickel catalyst. Alternatively, when X 5 is a halogen, then X 4 is a Grignard reagent, organotin, organomercury, boric acid or organoboron. By carrying out a coupling reaction using a metal, a metal compound or a metal catalyst such as a palladium catalyst or a nickel catalyst. A 9-arylindole derivative (Compound E) can be synthesized.
當X4及X5為鹵素或硫代氰酸酯時,則在9-位置上的碳及在10-位置上的碳被活化之蒽衍生物(化合物F)與具有反應活性碳之芳烴(化合物G)可藉由使用銅或銅化合物的Ullmann反應而偶合。在其中進行Ullmann反應的例子中,雖然X4及X5可彼此相同或不同,但是X4及X5較佳為碘。 When X 4 and X 5 are halogen or thiocyanate, the carbon at the 9-position and the carbon at the 10-position are activated with an anthracene derivative (compound F) and an aromatic hydrocarbon having a reactive carbon ( Compound G) can be coupled by Ullmann reaction using copper or a copper compound. In the example in which the Ullmann reaction is carried out, although X 4 and X 5 may be the same or different from each other, X 4 and X 5 are preferably iodine.
根據上述合成法,可合成以通式(1)代表的蒽衍生物。換言之,不同的取代基被各自引入蒽骨架的9-位置及10-位置中。 According to the above synthesis method, an anthracene derivative represented by the formula (1) can be synthesized. In other words, different substituents are each introduced into the 9-position and 10-position of the anthracene skeleton.
在其中合成不同的取代基被引入蒽骨架的9-位置及10-位置中的化合物的例子中,骨架通常一個接一個相繼偶合;因此使步驟數量增加,並不適合於工業。換言之,合成所花的時間變得比較長,並由於降低產率及類似因素而使成本增加。然而,當儘可能多的步驟數量被省略時(例如,在兩種骨架以一個階段同時引入蒽骨架的例子中),則預期會產生各種副產物且難以純化;因此不適合於工業。特別地,因為有機半導體材料的純度極為重要,所以當難以純化時,則有使材料特性大為降低的風險。 In the case of compounds in which different substituents are synthesized and introduced into the 9-position and 10-position of the anthracene skeleton, the skeletons are usually coupled one after another; thus increasing the number of steps is not suitable for industrial use. In other words, the time taken for the synthesis becomes longer, and the cost is increased by lowering the yield and the like. However, when as many steps as possible are omitted (for example, in the case where the two skeletons are simultaneously introduced into the anthracene skeleton in one stage), it is expected that various by-products are produced and it is difficult to purify; therefore, it is not suitable for the industry. In particular, since the purity of the organic semiconductor material is extremely important, when it is difficult to purify, there is a risk that the material properties are greatly lowered.
在本發明的合成法中,將欲引入蒽骨架中的骨架分開合成,並將骨架以2-3個步驟以1當量引入9-位置及10-位置中。在本發明的合成法中,反應係在每一階段以高產率進行,並抑制副產物的產生;因此,在考慮上述問題時,可將該方法視為最適合的方法。另外,該方法適合於大量合成,因為可抑制副產物,並可視為適合於工業的方法。 In the synthesis method of the present invention, the skeleton to be introduced into the anthracene skeleton is separately synthesized, and the skeleton is introduced into the 9-position and the 10-position in 1 to 2 steps in 1 to 3 steps. In the synthesis method of the present invention, the reaction is carried out in a high yield at each stage, and the generation of by-products is suppressed; therefore, when considering the above problems, the method can be regarded as the most suitable method. In addition, the method is suitable for a large amount of synthesis because by-products can be suppressed and can be regarded as a method suitable for industrial use.
再者,可省略用於獲得蒽衍生物(此為標的物)的合成階段,並且具有較高純度的蒽衍生物可以比慣例的方法更容易合成。此外,反應的時間期可縮短,其導致成本縮減。 Further, the synthesis stage for obtaining an anthracene derivative (this is the subject matter) can be omitted, and an anthracene derivative having a higher purity can be synthesized more easily than a conventional method. In addition, the time period of the reaction can be shortened, which leads to cost reduction.
本發明的蒽衍生物被敘述於此具體實施例模式中。 The anthracene derivatives of the present invention are described in this particular embodiment mode.
本發明的蒽衍生物為以通式(1)代表的蒽衍生物。 The anthracene derivative of the present invention is an anthracene derivative represented by the formula (1).
以通式(1)代表的蒽衍生物之9-及10-位置蒽骨架的被導入芳基以作為取代基。 The 9- and 10-position fluorene skeleton of the anthracene derivative represented by the general formula (1) is introduced into an aryl group as a substituent.
通常,因為具有高色彩純度的發藍光材料具有低的電 化學穩定性及低的激發態穩定性,所以使用發藍光材料的發光元件難以具有長壽命。因此,需要具有高色彩純度的發藍光材料之電化學穩定性及激發態穩定性來改善使用發藍光材料之發光元件的可靠度。而且,在發光元件中及在具有發光元件之發光裝置及電子裝置中,在考慮其中使用元件及裝置的各種外在環境時,特別必需對高溫的穩定性。 Usually, because of the high color purity, the blue light-emitting material has low electricity. Since chemical stability and low excited state stability are achieved, it is difficult to have a long life using a light-emitting element that emits a blue light-emitting material. Therefore, the electrochemical stability and the excited state stability of a blue light-emitting material having high color purity are required to improve the reliability of a light-emitting element using a blue light-emitting material. Further, in the light-emitting element and in the light-emitting device and the electronic device having the light-emitting element, stability against high temperature is particularly required in consideration of various external environments in which the element and the device are used.
已知蒽衍生物作為能夠發藍光的化合物;然而,蒽本身傾向形成固態準分子;因此,不可能獲得有效的發光,即使在蒽本身被用於發光元件的情況。再者,色度被減低。因此,必需引入大型取代基來避免形成準分子。特別地,有利的方法是引入取代基於9-及10-位置中,其為蒽最具反應性的位置。再者,為了保持蒽骨架的高載子傳輸性質,故特別有效的是引入芳基。以通式(1)代表的蒽衍生物可抑制準分子的形成,因為蒽衍生物的蒽骨架的9-及10-位置被導入芳基以作為取代基。再者,可維持載子傳輸性質。 Anthracene derivatives are known as compounds capable of emitting blue light; however, ruthenium itself tends to form solid excimers; therefore, it is impossible to obtain effective luminescence even in the case where ruthenium itself is used for a light-emitting element. Furthermore, the chromaticity is reduced. Therefore, it is necessary to introduce large substituents to avoid the formation of excimers. In particular, an advantageous method is to introduce substitutions based on the 9- and 10-positions, which are the most reactive sites for hydrazine. Further, in order to maintain the high carrier transport property of the anthracene skeleton, it is particularly effective to introduce an aryl group. The anthracene derivative represented by the formula (1) can suppress the formation of an excimer because the 9- and 10-positions of the anthracene skeleton of the anthracene derivative are introduced into the aryl group as a substituent. Furthermore, the carrier transport properties can be maintained.
另一方面,咔唑基具有其中將二苯胺基的苯基橋連的結構,所以含有咔唑基之化合物具有比含有二苯胺基之化合物更高的熱穩定性。因此,化合物的熱穩定性(玻璃轉換溫度或熔點)可藉由引入咔唑基而改善。再者,本發明者揭露:在使用其中引入一個咔唑基之化合物的例子中,例如其中將咔唑基只引入在二苯基蒽的一個苯基中的化合物,所增加的電化學穩定性比使用其中將咔唑基引入在二 苯基蒽的兩個苯基中的化合物更高。 On the other hand, the carbazolyl group has a structure in which a phenyl group of a diphenylamine group is bridged, so that the compound containing a carbazolyl group has higher thermal stability than a compound containing a diphenylamine group. Therefore, the thermal stability (glass transition temperature or melting point) of the compound can be improved by introducing a carbazolyl group. Further, the inventors have revealed that in the case of using a compound in which one carbazolyl group is introduced, for example, a compound in which a carbazolyl group is introduced only in one phenyl group of diphenylphosphonium, the electrochemical stability is increased. Introducing carbazole groups in two The compounds of the two phenyl groups of phenylhydrazine are higher.
換言之,本發明者揭露電化學穩定性係藉由將咔唑基只引入在一端的芳基中而大為改善。因此,本發明的特點為蒽衍生物在蒽的9-及10-位置之一上具有作為取代基的芳基及在另一位置上具有含咔唑基的芳基。另外,咔唑基較佳地具有其中在9-位置上的氮原子直接與芳基偶合的結構。 In other words, the inventors have revealed that electrochemical stability is greatly improved by introducing the carbazolyl group only into the aryl group at one end. Accordingly, the present invention is characterized in that the anthracene derivative has an aryl group as a substituent at one of the 9- and 10-positions of fluorene and an aryl group having a carbazole group at another position. Further, the carbazolyl group preferably has a structure in which a nitrogen atom at the 9-position is directly coupled to the aryl group.
具有上述結構之本發明的蒽衍生物具有極大的帶間隙;因此,具有短波長的發光是可能的,並可獲得具有高色彩純度的發藍光。 The anthracene derivative of the present invention having the above structure has an extremely large band gap; therefore, light emission having a short wavelength is possible, and blue light having high color purity can be obtained.
應注意,在本發明所提供的蒽衍生物中,芳基或烷基可包括在蒽骨架或與蒽骨架直接偶合的芳基中。這是基於下列的理由。 It should be noted that in the anthracene derivatives provided by the present invention, an aryl group or an alkyl group may be included in the anthracene skeleton or an aryl group directly coupled with the anthracene skeleton. This is based on the following reasons.
在發光元件中,材料結晶造成元件的資本損失。尤其,這是電極之間短路的直接原因,其抑制發光。因此。必需降低材料的結晶度。就此而言,有效的是引入適當的取代基至蒽骨架或與蒽骨架直接偶合的芳基中。芳基或烷基可被用作該等取代基。 In a light-emitting element, material crystallization causes a capital loss of the element. In particular, this is a direct cause of a short circuit between electrodes, which suppresses luminescence. therefore. It is necessary to reduce the crystallinity of the material. In this regard, it is effective to introduce an appropriate substituent into the anthracene skeleton or an aryl group directly coupled to the anthracene skeleton. An aryl group or an alkyl group can be used as the substituents.
被引入的芳基或烷基沒有限制;然而,以苯基、鄰-聯苯基或類似物作為芳基較佳,而以甲基、第三丁基或類似物作為烷基較佳。 The aryl group or alkyl group to be introduced is not limited; however, a phenyl group, an o-biphenyl group or the like is preferred as the aryl group, and a methyl group, a tert-butyl group or the like is preferably used as the alkyl group.
烷基具有極大的結晶抑制效果,並可抑制無法藉由引入芳基而抑制結晶的結構之結晶。應注意引入烷基可能減低載子傳輸性質;因此,在欲引入取代基之物質的結晶度 不太高的例子中,以維持載子傳輸性質為角度,以芳基作為欲引入之取代基更有效。 The alkyl group has an extremely large crystallization inhibiting effect, and can suppress crystallization of a structure which cannot suppress crystallization by introducing an aryl group. It should be noted that the introduction of an alkyl group may reduce the carrier transport properties; therefore, the crystallinity of the substance to which the substituent is to be introduced In a less high case, it is more effective to use an aryl group as a substituent to be introduced in order to maintain the carrier transport property.
以上述通式(1)代表的本發明的蒽衍生物之典型實例顯示在下列結構式(11)至(53)、結構式(61)至(76)及結構式(81)至(90)中。當然本發明不限於此。 Typical examples of the anthracene derivatives of the present invention represented by the above formula (1) are shown in the following structural formulae (11) to (53), structural formulae (61) to (76), and structural formulas (81) to (90). in. Of course, the invention is not limited thereto.
本發明的蒽衍生物具有高的電化學穩定性。再者,本發明的蒽衍生物具有高的熱穩定性。再者,本發明的蒽衍生物具有極大的帶間隙;因此,當被用作發光元件的發光層中的主體時,可獲得具有高色彩純度的發藍光。再者,本發明的蒽衍生物具有極大的帶間隙;因此,在被用作發光元件的發光層中的摻雜物時,可獲得具有高色彩純度的發藍光。使用根據本發明的蒽衍生物之發光元件可具有高可靠度。尤其當本發明的蒽衍生被用作發光元件的發光層中的主體及摻雜物時,均可獲得具有極高的可靠度之發光元件。 The anthracene derivatives of the invention have high electrochemical stability. Further, the anthracene derivative of the present invention has high thermal stability. Further, the anthracene derivative of the present invention has an extremely large band gap; therefore, when used as a main body in the light-emitting layer of the light-emitting element, blue light having high color purity can be obtained. Further, the anthracene derivative of the present invention has an extremely large band gap; therefore, when used as a dopant in the light-emitting layer of the light-emitting element, blue light having high color purity can be obtained. The light-emitting element using the anthracene derivative according to the present invention can have high reliability. Particularly when the ruthenium derivative of the present invention is used as a host and a dopant in the light-emitting layer of the light-emitting element, a light-emitting element having extremely high reliability can be obtained.
以上述結構式(11)至(53)、結構式(61)至(76)及結構式(81)至(90)所代表的蒽衍生物可使用在具體實施例模式1中所述之合成法合成。 The anthracene derivatives represented by the above structural formulas (11) to (53), structural formulae (61) to (76) and structural formulas (81) to (90) can be synthesized as described in the specific embodiment mode 1. Method synthesis.
使用本發明的蒽衍生物之發光元件的模式以參考圖1A至1C及圖2敘述於此具體實施例模式中。 The mode of the light-emitting element using the anthracene derivative of the present invention is described in this embodiment mode with reference to Figs. 1A to 1C and Fig. 2.
本發明的發光元件在一對電極之間具有數層。該數層係藉由組合由具有高載子注射性質之物質或具有高載子傳輸性質之物質所形成的層而堆疊得到,所以發光區域形成於與電極分開的地方,換言之,載子係在與電極分開的部位重組合。在本發明的說明書中,在介於一對電極之間所形成的數層在此被稱為EL層。 The light-emitting element of the present invention has several layers between a pair of electrodes. The number of layers is obtained by stacking layers formed of substances having high carrier injection properties or substances having high carrier transport properties, so that the light-emitting region is formed at a position separate from the electrodes, in other words, the carrier is The parts separated from the electrodes are recombined. In the specification of the present invention, a plurality of layers formed between a pair of electrodes are referred to herein as EL layers.
在此具體實施例模式中,發光元件包括相繼堆疊的第 一個電極102、第一層103、第二層104、第三層105、第四層106及第二個電極107。應注意此具體實施例模式係在第一個電極102充當陽極及第二個電極107充當陰極的條件下敘述於下文。 In this embodiment mode, the illuminating element comprises a plurality of successively stacked An electrode 102, a first layer 103, a second layer 104, a third layer 105, a fourth layer 106, and a second electrode 107. It should be noted that this particular embodiment mode is described below under the condition that the first electrode 102 acts as an anode and the second electrode 107 acts as a cathode.
基板101被用作發光元件的支撐底板。可使用例如玻璃、塑膠或類似物為基板101。應注意可使用其他材料,只要其充當在發光元件的製造法中的支撐底板即可。 The substrate 101 is used as a support substrate for a light-emitting element. A substrate 101 such as glass, plastic or the like can be used. It should be noted that other materials may be used as long as they serve as a support substrate in the manufacturing method of the light-emitting element.
較佳地使用具有高功函數(尤其為4.0eV或更高)的金屬、合金、導電性化合物、其混合物或類似物作為第一個電極102。尤其可使用氧化銦-氧化錫(ITO:氧化銦錫)、含有矽或氧化矽之氧化銦-氧化錫、氧化銦-氧化鋅(IZO:氧化銦鋅)、含有氧化鎢及氧化鋅之氧化銦(IWZO)或類似物。雖然該等導電性金屬氧化物薄膜通常係由濺鍍所形成,但是彼等可藉由施予溶膠-凝膠法或類似方法所形成。例如,氧化銦-氧化鋅(IZO)膜可藉由濺鍍法形成,其係使用其中1至20重%之氧化鋅被加入氧化銦中的標靶。含有氧化鎢及氧化鋅之氧化銦(IWZO)膜可藉由濺鍍法形成,其係使用其中0.5至5重量%之氧化鎢及0.1至1重量%之氧化鋅被包括在氧化銦中的標靶。另外,可提供金(Au)、鉑(Pt)、鎳(Ni)、鎢(W)、鉻(Cr)、鉬(Mo)、鐵(Fe)、鈷(Co)、銅(Cu)、鈀(Pd)、金屬材料之氮化物(如氮化鈦:TiN)或類似物。 As the first electrode 102, a metal, an alloy, a conductive compound, a mixture thereof or the like having a high work function (especially 4.0 eV or higher) is preferably used. In particular, indium oxide-tin oxide (ITO: indium tin oxide), indium oxide-tin oxide containing antimony or antimony oxide, indium oxide-zinc oxide (IZO: indium zinc oxide), indium oxide containing tungsten oxide and zinc oxide can be used. (IWZO) or the like. Although the conductive metal oxide thin films are usually formed by sputtering, they may be formed by applying a sol-gel method or the like. For example, an indium oxide-zinc oxide (IZO) film can be formed by a sputtering method using a target in which 1 to 20% by weight of zinc oxide is added to indium oxide. An indium oxide (IWZO) film containing tungsten oxide and zinc oxide can be formed by a sputtering method using 0.5 to 5% by weight of tungsten oxide and 0.1 to 1% by weight of zinc oxide included in the indium oxide. target. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium may be provided. (Pd), a nitride of a metal material (such as titanium nitride: TiN) or the like.
第一層103為含有具有高電洞注射性質之物質的層。 可使用氧化鉬(MoOX)、氧化釩(VOX)、氧化釕(RuOX)、氧化鎢(WOX)、氧化錳(MnOX)或類似物。或者,第一層103可使用酞花青(縮寫:H2Pc);以酞花青為主之化合物,如酞花青銅(縮寫:CuPc);芳香族胺化合物,如4,4’-雙〔N-(4-二苯胺基苯基)-N-苯胺基〕聯苯(縮寫:DPAB)或4,4’-雙(N-{4-〔N-(3-甲苯基)-N-苯胺基〕苯基}-N-苯胺基)聯苯(縮寫:DNTPD);或高分子材料,如聚(伸乙二氧基噻吩)/聚(苯乙烯磺酸)(PEDOT/PSS)或類似物形成。 The first layer 103 is a layer containing a substance having high hole injection properties. Molybdenum oxide (MoO X ), vanadium oxide (VO X ), ruthenium oxide (RuO X ), tungsten oxide (WO X ), manganese oxide (MnO X ) or the like can be used. Alternatively, the first layer 103 may use phthalocyanine (abbreviation: H 2 Pc); a compound mainly composed of phthalocyanine, such as sassafras bronze (abbreviation: CuPc); an aromatic amine compound such as 4, 4'-double [N-(4-Diphenylaminophenyl)-N-anilino]biphenyl (abbreviation: DPAB) or 4,4'-bis(N-{4-[N-(3-methylphenyl)-N- Anilino]phenyl}-N-anilinobiphenyl (abbreviation: DNTPD); or a polymeric material such as poly(ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS) or the like Object formation.
或者,組合有機化合物與無機化合物所形成的複合材料可用於第一層103。特別地,含有機化合物及無機化合物之複合材料具有關於有機化合物的電子接受性質,具有極佳的電洞注射性質及電洞傳輸性質,因為電子在介於有機化合物與無機化合物之間轉移,並使載子密度增加。 Alternatively, a composite material formed by combining an organic compound and an inorganic compound may be used for the first layer 103. In particular, a composite material containing an organic compound and an inorganic compound has an electron accepting property with respect to an organic compound, and has excellent hole injection properties and hole transport properties because electrons are transferred between an organic compound and an inorganic compound, and Increase the carrier density.
在使用由組合有機化合物與無機化合物所形成的複合材料於第一層103的例子中,第一層103可達成與第一個電極102的歐姆接觸;因此,第一個電極材料的選擇無關於功函數。 In the example in which the composite material formed by combining the organic compound and the inorganic compound is used in the first layer 103, the first layer 103 can achieve ohmic contact with the first electrode 102; therefore, the selection of the first electrode material is not relevant. Work function.
較佳地使用過渡金屬之氧化物作為用於複合材料的無機化合物。而且,可使用週期表第4至8族之金屬的氧化物。尤其,較佳的是使用氧化釩、氧化鈮、氧化鉭、氧化鉻、氧化鉬、氧化鎢、氧化錳及氧化銠,因為彼等高的電子接受性質。在彼等之中,以氧化鉬特別佳,因為其在空氣下穩定,具有低吸濕性質及容易處理。 An oxide of a transition metal is preferably used as the inorganic compound for the composite material. Further, an oxide of a metal of Groups 4 to 8 of the periodic table can be used. In particular, it is preferred to use vanadium oxide, cerium oxide, cerium oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide and cerium oxide because of their high electron accepting properties. Among them, molybdenum oxide is particularly preferred because it is stable under air, has low hygroscopic properties and is easy to handle.
可使用各種例如芳香族胺氧化合物、咔唑衍生物、芳香族烴及高分子化合物(如寡聚物、樹枝狀聚合物或聚合物)的化合物作為用於複合材料之有機化合物。用於複合材料的有機化合物較佳為具有高電洞傳輸性質的有機化合物。尤其,較佳地使用具有大於或等於10-6平方公分/伏特秒之電洞遷移率的物質。然而,也可使用除了該等物質之外的其他材料,只要其電洞傳輸性質大於其電子傳輸性質即可。可用於複合材料之有機化合物特別顯示於下。 As the organic compound for the composite material, various compounds such as an aromatic amine oxygen compound, a carbazole derivative, an aromatic hydrocarbon, and a polymer compound such as an oligomer, a dendrimer or a polymer can be used. The organic compound used for the composite material is preferably an organic compound having high hole transport properties. In particular, a substance having a hole mobility of greater than or equal to 10 -6 cm 2 /volt second is preferably used. However, other materials than those may be used as long as their hole transport properties are greater than their electron transport properties. Organic compounds which can be used in composite materials are particularly shown below.
例如,可使用下列作為芳香族胺化合物:N,N’-二(對-甲苯基)-N,N’-二苯基-對-苯二胺(縮寫:DTDPPA)、4,4’-雙〔N-(4-二苯胺基苯基)-N-苯胺基〕聯苯(縮寫:DPAB)、4,4’-雙(N-{4-〔N-(3-甲苯胺)-N-苯胺基〕苯基}-N-苯胺基)聯苯(縮寫:DNTPD)、1,3,5-參〔N-(4-二苯胺基苯基)-N-苯胺基〕苯(縮寫:DPA3B)及類似物。 For example, the following may be used as the aromatic amine compound: N,N'-bis(p-tolyl)-N,N'-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4'-double [N-(4-Diphenylaminophenyl)-N-anilino]biphenyl (abbreviation: DPAB), 4,4'-bis(N-{4-[N-(3-toluidine)-N- Anilino]phenyl}-N-anilino)biphenyl (abbreviation: DNTPD), 1,3,5-gin[N-(4-diphenylaminophenyl)-N-anilino]benzene (abbreviation: DPA3B ) and the like.
尤其可使用下列作為可用於複合材料的咔唑衍生物:3-〔N-(9-苯基咔唑-3-基)-N-苯胺基〕-9-苯基咔唑(縮寫:PCzPCA1)、3,6-雙〔N-(9-苯基咔唑-3-基)-N-苯胺基〕-9-苯基咔唑(縮寫:PCzPCA2)、3-〔N-(1-萘基)-N-(9-苯基咔唑-3-基)胺基〕-9-苯基咔唑(縮寫:PCzPCN1);及類似物。 In particular, the following can be used as a carbazole derivative which can be used for a composite material: 3-[N-(9-phenyloxazol-3-yl)-N-anilino]-9-phenylcarbazole (abbreviation: PCzPCA1) ,3,6-bis[N-(9-phenyloxazol-3-yl)-N-anilino]-9-phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl) -N-(9-phenyloxazol-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1); and the like.
此外,可使用下列作為可用於複合材料的咔唑衍生物:4,4’-二(N-咔唑基)聯苯(縮寫:CBP)、1,3,5-參〔4-(N-咔唑基)苯基〕苯(縮寫:TCPB)、9-〔4-(N- 咔唑基)〕苯基-10-苯蒽(縮寫:CzPA)、1,4-雙〔4-(N-咔唑基)苯基〕-2,3,5,6-四苯基苯;或類似物。 In addition, the following can be used as the carbazole derivative which can be used for the composite material: 4,4'-bis(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3,5-gin [4-(N- Carbazolyl)phenyl]benzene (abbreviation: TCPB), 9-[4-(N- Benzazolyl)]phenyl-10-benzoquinone (abbreviation: CzPA), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene; Or similar.
可使用例如下列作為可用於複合材料的芳香族烴:2-第三丁基-9,10-二(2-萘基)蒽(縮寫:t-BuDNA);2-第三丁基-9,10-二(1-萘基)蒽;9,10-雙(3,5-二苯基苯基)蒽(縮寫:DPPA);2-第三丁基-9,10-雙(4-苯基苯基)蒽(縮寫:t-BuDBA);9,10-二(2-萘基)蒽(縮寫:DNA);9,10-二苯蒽(縮寫:DPAnth);2-第三丁蒽(縮寫:t-BuAnth);9,10-雙(4-甲基-1-萘基)蒽(縮寫:DMNA);2-第三丁基-9,10-雙〔2-(1-萘基)苯基〕蒽;9,10-雙〔2-(1-萘基)苯基〕蒽;2,3,6,7-四甲基-9,10-二(1-萘基)蒽;2,3,6,7-四甲基-9,10-二(2-萘基)蒽;9,9’-聯萘;10,10’-二苯基-9,9’-聯萘;10,10’-雙(2-苯基苯基)-9,9’-聯萘;10,10’-雙〔(2,3,4,5,6-五苯基)苯基〕-9,9’-聯萘;蒽;四環素;紅螢烯;苝;2,5,8,11-四(第三丁基)苝及類似物。除了該等化合物之外,也可使用五環素、暈苯(coronene)或類似物。特別地,以具有大於或等於10-6平方公分/伏特秒之電洞遷移率及具有10至42個碳原子之芳香族烴更佳。 For example, the following can be used as an aromatic hydrocarbon which can be used for a composite material: 2-t-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA); 2-tert-butyl-9, 10-bis(1-naphthyl)anthracene; 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA); 2-tert-butyl-9,10-bis(4-benzene Phenyl phenyl) hydrazine (abbreviation: t-BuDBA); 9,10-bis(2-naphthyl) fluorene (abbreviation: DNA); 9,10-diphenylhydrazine (abbreviation: DPAnth); 2-third butyl (abbreviation: t-BuAnth); 9,10-bis(4-methyl-1-naphthyl)anthracene (abbreviation: DMNA); 2-tert-butyl-9,10-bis[2-(1-naphthalene) Phenyl]anthracene; 9,10-bis[2-(1-naphthyl)phenyl]anthracene; 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene ; 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene; 9,9'-binaphthyl;10,10'-diphenyl-9,9'-binaphthyl10,10'-bis(2-phenylphenyl)-9,9'-binaphthyl;10,10'-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-binaphthyl;anthracene;tetracycline; red fluorene; anthracene; 2,5,8,11-tetra(t-butyl)anthracene and the like. In addition to these compounds, pentacyclin, coronene or the like can also be used. In particular, it is more preferable to have a hole mobility of 10 -6 cm 2 /volt second or more and an aromatic hydrocarbon having 10 to 42 carbon atoms.
可用於複合材料的芳香族烴可具有乙烯基骨架。可使用例如下列作為具有乙烯基之芳香族烴:4,4’-雙(2,2-二苯基乙烯基)聯苯(縮寫:DPVBi);9,10-雙〔4-(2,2-二苯基乙烯基)苯基〕蒽(縮寫:DPVPA);及類似物。 The aromatic hydrocarbons useful in the composite may have a vinyl skeleton. For example, the following may be used as the aromatic hydrocarbon having a vinyl group: 4,4'-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi); 9,10-bis[4-(2,2) -Diphenylvinyl)phenyl]indole (abbreviation: DPVPA); and analogs.
而且,也可使用高分子化合物,如聚(N-乙烯基咔 唑)(縮寫:PVK)或聚(4-乙烯基三苯胺)(縮寫:PVTPA)。 Moreover, a polymer compound such as poly(N-vinyl anthracene) can also be used. Oxazole) (abbreviation: PVK) or poly(4-vinyltriphenylamine) (abbreviation: PVTPA).
以具有高電洞傳輸性質之物質作為形成第二層104的物質較佳,尤其為芳香族胺化合物(即具有苯環-氮鍵之化合物)。可使用4,4’-雙〔N-(3-甲苯基)-N-苯胺基〕聯苯、其衍生物,如4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(以下被稱為NPB)及星爆式芳香族胺化合物,如4,4’,4”-參(N,N-二苯胺基)三苯胺及4,4’,4”-參〔N-(3-甲苯基)-N-苯胺基〕三苯胺作為被廣泛使用的材料。本文所述之該等材料主要為分別具有大於或等於10-6平方公分/伏特秒之電洞遷移率的物質。然而,也可使用除了該等化合物之外的其他材料,只要其電洞傳輸性質大於其電子傳輸性質即可。第二層104不限於單層,並可使用前述物質的混合層或具有分別含有前述物質的二或多層之堆疊層。 As the substance forming the second layer 104, a substance having a high hole transport property is preferable, particularly an aromatic amine compound (i.e., a compound having a benzene ring-nitrogen bond). 4,4'-bis[N-(3-tolyl)-N-anilino]biphenyl, a derivative thereof such as 4,4'-bis[N-(1-naphthyl)-N-aniline can be used. Biphenyl (hereinafter referred to as NPB) and starburst aromatic amine compounds such as 4,4',4"-parade (N,N-diphenylamino)triphenylamine and 4,4',4"- [N-(3-Tolyl)-N-anilino]triphenylamine is widely used as a material. The materials described herein are primarily materials having a mobility of holes greater than or equal to 10-6 square centimeters per volt second, respectively. However, other materials than the compounds may be used as long as their hole transport properties are greater than their electron transport properties. The second layer 104 is not limited to a single layer, and a mixed layer of the foregoing substances or a stacked layer having two or more layers each containing the foregoing substances may be used.
第三層105為含有發光物質的層。在此具體實施例模式中,第三層105包括在具體實施例模式1中所述之本發明的蒽衍生物。本發明的蒽衍生物可有利於作為發光物質而塗覆於發光元件,因為本發明的蒽衍生物能夠發出具有短波長之光及展現具有高色彩純度的發藍光。 The third layer 105 is a layer containing a luminescent substance. In this embodiment mode, the third layer 105 comprises the anthracene derivative of the present invention as described in the specific embodiment mode 1. The anthracene derivative of the present invention can be favorably applied as a luminescent substance to a light-emitting element because the anthracene derivative of the present invention can emit light having a short wavelength and exhibit blue light having a high color purity.
可使用具有高的電子傳輸性質之物質作為第四層106。例如,可使用含有具有喹啉或苯並喹啉骨架之金屬錯合物或類似物的層,如參(8-喹啉)絡鋁(縮寫:Alq)、參(4-甲基-8-喹啉)絡鋁(縮寫:Almq3)、雙 (10-羥基苯並〔h〕喹啉)絡鈹(縮寫:BeBq2)或雙(2-甲基-8-喹啉)(4-苯基酚)絡鋁(縮寫:BAlq)。或者,可使用具有以噁唑為主或噻唑為主之配位基的金屬錯合物或類似物,如雙〔2-(2-羥苯基)苯並噁唑〕絡鋅(縮寫:Zn(BOX)2)或雙〔2-(2-羥苯基)苯並噻唑〕絡鋅(縮寫:Zn(BTZ)2)。除了金屬錯合物之外,也可使用2-(4-聯苯基)-5-(4-第三丁苯基)-1,3,4-噁二唑(縮寫:PBD)、1,3-雙〔5-(對-第三丁苯基)-1,3,4-噁二唑-2-基〕苯(縮寫:OXD-7)、3-(4-聯苯基)-4-苯基-5-(4-第三丁苯基)-1,2,4-三唑(縮寫:TAZ)、二苯啡咯啉(縮寫:BPhen)、浴靈銅(bathocuproine)(縮寫:BCP)或類似物。本文所述之物質主要為分別具有大於或等於10-6平方公分/伏特秒之電洞遷移率的物質。電子傳輸層可使用除了上述該等之外的其他材料形成,只要該材料具有比電洞傳輸性質更高的電子傳輸性質即可。此外,電子傳輸層不限於單層,並可堆疊其中每一層係由前述物質所製得的二或多層。 As the fourth layer 106, a substance having high electron transport properties can be used. For example, a layer containing a metal complex or the like having a quinoline or benzoquinoline skeleton such as ginseng (8-quinoline) complex aluminum (abbreviation: Alq), ginseng (4-methyl-8-) may be used. Quinoline) aluminum (abbreviation: Almq 3 ), bis(10-hydroxybenzo[h]quinoline) oxime (abbreviation: BeBq 2 ) or bis(2-methyl-8-quinoline) (4-benzene) Alkyl phenol) aluminum (abbreviation: BAlq). Alternatively, a metal complex or the like having a oxazole-based or thiazole-based ligand such as bis[2-(2-hydroxyphenyl)benzoxazole] complex zinc (abbreviation: Zn) may be used. (BOX) 2 ) or bis[2-(2-hydroxyphenyl)benzothiazole] complex zinc (abbreviation: Zn(BTZ) 2 ). In addition to the metal complex, 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1, can also be used. 3-bis[5-(p-t-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 3-(4-biphenyl)-4 -Phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), diphenylmorpholine (abbreviation: BPhen), bathocuproine (abbreviation: BCP) or the like. The materials described herein are primarily those having a mobility of holes greater than or equal to 10 -6 cm 2 / volt second, respectively. The electron transport layer may be formed using other materials than those described above as long as the material has higher electron transport properties than hole transport properties. Further, the electron transport layer is not limited to a single layer, and each of the layers may be stacked in two or more layers made of the foregoing substances.
較佳地使用具有低功函數(尤其為3.8eV或更低)之金屬、合金、導電性化合物、其混合物或類似物作為形成第二個電極107的物質。可使用屬於週期表中的第1族或第2族之元素,即鹼金屬,如鋰(Li)或銫(Cs)、鹼土金屬,如鎂(Mg)、鈣(Ca)或鍶(Sr),含有該等金屬之合金(MgAg,AlLi)作為該陰極材料的特殊實例。稀土金屬,如銪(Eu)或鐿(Yb)、含有該等稀土 金屬之合金或類似物也適合。然而,藉由在介於第二個電極107與第四層106之間提供具有促進電子注射功能的層,得以與第二電極堆疊,各種導電性材料,如Al、Ag、ITO或含有矽或氧化矽的ITO可用於第二個電極107,無關於功函數的大小。 As the material forming the second electrode 107, a metal, an alloy, a conductive compound, a mixture thereof or the like having a low work function (especially 3.8 eV or less) is preferably used. An element belonging to Group 1 or Group 2 of the periodic table may be used, that is, an alkali metal such as lithium (Li) or cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) or strontium (Sr). An alloy containing these metals (MgAg, AlLi) is a special example of the cathode material. a rare earth metal such as Eu (Eu) or Yb (Yb) containing such rare earths Metal alloys or the like are also suitable. However, by providing a layer having a function of promoting electron injection between the second electrode 107 and the fourth layer 106, it is possible to stack with the second electrode, and various conductive materials such as Al, Ag, ITO or contain germanium or The ITO of yttria can be used for the second electrode 107 regardless of the size of the work function.
可使用鹼金屬、鹼土金屬或其化合物,如氟化鋰(LiF)、氟化銫(CsF)或氟化鈣(CaF2)作為具有促進電子注射功能的層。例如,可使用含有具有電子傳輸性質之物質及鹼金屬、鹼土金屬或其化合物(例如,Alq包括鎂(Mg))的層。較佳的是使用該層,因為使來自第二個電極107的電子注射有效地進行。 An alkali metal, an alkaline earth metal or a compound thereof such as lithium fluoride (LiF), cesium fluoride (CsF) or calcium fluoride (CaF 2 ) can be used as the layer having a function of promoting electron injection. For example, a layer containing a substance having electron transporting property and an alkali metal, an alkaline earth metal or a compound thereof (for example, Alq including magnesium (Mg)) may be used. It is preferable to use the layer because the electron injection from the second electrode 107 is efficiently performed.
可使用各種方法形成第一層103、第二層104、第三層105及第四層106。例如,可使用蒸發法、噴墨法、旋塗法或類似方法。此外,每一電極或每一層可以不同的膜形成方法形成。 The first layer 103, the second layer 104, the third layer 105, and the fourth layer 106 can be formed using various methods. For example, an evaporation method, an inkjet method, a spin coating method, or the like can be used. Further, each electrode or each layer may be formed by a different film formation method.
由於在第一個電極102與第二個電極107之間產生不同的電位而使電流流動,使得電洞及電子在具有高發光性質之物質的第三層中重組,其導致來自本發明的發光元件之發光。換言之,本發明的發光元件具有發光區形成於第三層105中的結構。 Since a different potential is generated between the first electrode 102 and the second electrode 107, current flows, so that holes and electrons recombine in the third layer of the substance having high luminescent properties, which results in luminescence from the present invention. The illumination of the component. In other words, the light-emitting element of the present invention has a structure in which the light-emitting region is formed in the third layer 105.
發光係經由第一個電極102及第二個電極107之一或二者向外萃取出。因此,第一個電極102及第二個電極107之一或二者係使用具有光傳送性質的電極所形成。在其中只有第一個電極102為具有光傳送性質之電極的例子 中,發光係從基板面經由第一個電極102萃取出,如圖1A所示。或者,在其中只有第二個電極107為具有光傳送性質之電極的例子中,發光係從基板的反面經由第二個電極107萃取出,如圖1B所示。在其中第一個電極102及第二個電極107二者為具有光傳送性質之電極的例子中,發光係從基板面及基板的反面二者經由第一個電極102及第二個電極107萃取出,如圖1C所示。 The illumination is extracted outward through one or both of the first electrode 102 and the second electrode 107. Therefore, one or both of the first electrode 102 and the second electrode 107 are formed using an electrode having light transmitting properties. An example in which only the first electrode 102 is an electrode having optical transmission properties The light emission is extracted from the substrate surface via the first electrode 102 as shown in FIG. 1A. Alternatively, in the example in which only the second electrode 107 is an electrode having light transmitting properties, the light emitting system is extracted from the reverse side of the substrate via the second electrode 107 as shown in FIG. 1B. In an example in which both the first electrode 102 and the second electrode 107 are electrodes having optical transmission properties, the luminescence is extracted from both the substrate surface and the reverse side of the substrate via the first electrode 102 and the second electrode 107. Out, as shown in Figure 1C.
在介於第一個電極102與第二個電極107之間所提供的層之結構不限於上述結構。可使用除了上述結構之外的結構,只要其中電洞與電子重組的發光區位於遠離第一個電極102及第二個電極107處即可,以阻止由於發光區附近及金屬的驟冷。 The structure of the layer provided between the first electrode 102 and the second electrode 107 is not limited to the above structure. A structure other than the above structure may be used as long as the light-emitting region in which the hole and the electron recombines are located away from the first electrode 102 and the second electrode 107 to prevent quenching due to the vicinity of the light-emitting region and the metal.
換言之,層的堆疊結構未被特別限制成上述結構,並且使用具有高電子傳輸性質之物質、具有高電洞傳輸性質之物質、具有高電子注射性質之物質、具有高電洞注射性質之物質、雙極性物質(具有高電子傳輸性質及高電洞傳輸性質之物質)、電洞封閉材料或類似物所形成的層可與本發明的蒽衍生物自由組合。 In other words, the stacked structure of the layers is not particularly limited to the above structure, and a substance having high electron transporting property, a substance having high hole transporting property, a substance having high electron injecting property, a substance having high hole injecting property, A layer formed of a bipolar substance (a substance having high electron transport properties and high hole transport properties), a hole blocking material or the like can be freely combined with the anthracene derivative of the present invention.
在圖2所示之發光元件具有其中充當陰極的第一個電極302、使用具有高電子傳輸性質之物質所形成的第一層303、含有發光物質的第二層304、使用具有高電洞傳輸性質之物質所形成的第三層305、使用具有高電子注射性質之物質所形成的第四層306及充當陽極的第二個電極307相繼堆疊於基板301上的結構。 The light-emitting element shown in Fig. 2 has a first electrode 302 serving as a cathode, a first layer 303 formed using a substance having high electron transporting property, a second layer 304 containing a light-emitting substance, and having a high hole transmission. The third layer 305 formed of the substance of the nature, the fourth layer 306 formed using a substance having high electron injecting property, and the second electrode 307 serving as an anode are successively stacked on the substrate 301.
在此具體實施例模式中,發光元件係在由玻璃、塑膠或類似物所製得的基板上製造。被動式矩陣發光裝置可藉由在一個基板上製造數個上述的發光元件而製造。或者,例如薄膜電晶體(IFT)可在由玻璃、塑膠或類似物所製得的基板上形成,而發光元件可在與TFT以電連接的電極上製造。因此,可製造主動式矩陣發光裝置,其中發光元件的驅動受到TFT控制。TFT的結構沒有嚴格的限制,並且TFT可為交錯型TFT或反轉交錯型TFT。用於TFT之半導體的結晶度也沒有限制,並可使用非晶形半導體或結晶狀半導體。另外,在TFT基板上所形成的驅動電路可使用N-型TFT及P-型TFT形成,或可使用N-型TFT及P-型TFT中任一者形成。 In this embodiment mode, the light-emitting elements are fabricated on a substrate made of glass, plastic or the like. Passive matrix light-emitting devices can be fabricated by fabricating a plurality of the above-described light-emitting elements on a single substrate. Alternatively, for example, a thin film transistor (IFT) may be formed on a substrate made of glass, plastic or the like, and a light-emitting element may be fabricated on an electrode electrically connected to the TFT. Therefore, an active matrix light-emitting device can be manufactured in which the driving of the light-emitting elements is controlled by the TFT. The structure of the TFT is not strictly limited, and the TFT may be a staggered TFT or an inverted staggered TFT. The crystallinity of the semiconductor used for the TFT is also not limited, and an amorphous semiconductor or a crystalline semiconductor can be used. Further, the driving circuit formed on the TFT substrate may be formed using an N-type TFT and a P-type TFT, or may be formed using any of an N-type TFT and a P-type TFT.
如在此具體實施例模式中所示,本發明的蒽衍生物可用於發光層,如在此具體實施例模式中所示,沒有加入任何其他的發光物質,因為蒽衍生物發出高純度的藍光。 As shown in this specific embodiment mode, the anthracene derivative of the present invention can be used for the light-emitting layer, as shown in the embodiment mode, without adding any other light-emitting substance because the anthracene derivative emits high-purity blue light. .
因為本發明的蒽衍生物具有高發光效率,所以具有高發光效率之發光元件可藉由在發光元件中使用本發明的蒽衍生物而獲得。具有高可靠度的發光元件也可藉由在發光元件中使用本發明的蒽衍生物而獲得。 Since the anthracene derivative of the present invention has high luminous efficiency, a light-emitting element having high luminous efficiency can be obtained by using the anthracene derivative of the present invention in a light-emitting element. A light-emitting element having high reliability can also be obtained by using the anthracene derivative of the present invention in a light-emitting element.
因為使用本發明的蒽衍生物之發光元件能夠發出具有高色彩純度的藍光,所以可有利地用於全彩顯示器。再者,使用本發明的蒽衍生物之發光元件達成發出具有高可靠度的藍光之能力允許其在全彩顯示器中的應用。 Since the light-emitting element using the anthracene derivative of the present invention can emit blue light having high color purity, it can be advantageously used for a full-color display. Furthermore, the use of the luminescent element of the hydrazine derivative of the present invention to achieve the ability to emit blue light with high reliability allows its use in full color displays.
具有不同於具體實施例模式3中所示之結構的發光元件被敘述於此具體實施例模式中。 A light-emitting element having a structure different from that shown in the embodiment mode 3 is described in this embodiment mode.
所形成之具體實施例模式3中所示之第三層105具有本發明的蒽衍生物被分散在另一物質中的結構,藉此可獲得來自本發明的蒽衍生物之發光。因為本發明的蒽衍生物展現具有高色彩純度的發藍光,所以可獲得展現具有高色彩純度的發藍光之發光元件。 The third layer 105 shown in the specific embodiment mode 3 formed has a structure in which the anthracene derivative of the present invention is dispersed in another substance, whereby the luminescence from the anthracene derivative of the present invention can be obtained. Since the anthracene derivative of the present invention exhibits blue light having high color purity, a blue light-emitting element exhibiting high color purity can be obtained.
在此,較佳地使用具有帶間隙比本發明的蒽衍生物更大的物質作為分散本發明的蒽衍生物之物質。尤其可使用低分子化合物,如4,4’,4”-三(N-咔唑基)三苯胺(縮寫:TCTA)、1,1-雙〔4-(二苯胺基)苯基〕環己烷(縮寫:TPAC)、9,9-雙〔4-(二苯胺基)苯基〕茀(縮寫:TPAF)、4,4’-二(N-咔唑基)聯苯(縮寫:CBP)、1,3-雙〔5-(對-第三丁苯基)-1,3,4-噁二唑-2-基〕苯(縮寫:OXD-7)、2,2’,2”-(1,3,5-苯三基)參(1-苯基-1H-苯並咪唑)(縮寫:TPBI)、3-(4-第三丁苯基)-4-苯基-5-(4-聯苯基)-1,2,4-三唑(縮寫:TAZ),或高分子化合物,如聚(N-乙烯基咔唑)(縮寫:PVK)、聚(4-乙烯基三苯胺)(縮寫:PVTPA)或聚(2,5-吡啶二基)(縮寫:PPy)。 Here, a substance having a larger gap than the anthracene derivative of the present invention is preferably used as a substance for dispersing the anthracene derivative of the present invention. In particular, low molecular compounds such as 4,4',4"-tris(N-carbazolyl)triphenylamine (abbreviation: TCTA), 1,1-bis[4-(diphenylamino)phenyl]cyclohexane can be used. Alkane (abbreviation: TPAC), 9,9-bis[4-(diphenylamino)phenyl]anthracene (abbreviation: TPAF), 4,4'-di(N-carbazolyl)biphenyl (abbreviation: CBP) , 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 2,2', 2"- (1,3,5-benzenetriyl) ginseng (1-phenyl-1H-benzimidazole) (abbreviation: TPBI), 3-(4-t-butylphenyl)-4-phenyl-5-( 4-biphenyl)-1,2,4-triazole (abbreviation: TAZ), or a polymer compound such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA) or poly(2,5-pyridinediyl) (abbreviation: PPy).
因為本發明的蒽衍生物能夠藉由使用發光元件用的蒽衍生物而發出具有高色彩純度的藍光,所以可獲得展現具有高色彩純度的發藍光之發光元件。 Since the anthracene derivative of the present invention can emit blue light having high color purity by using an anthracene derivative for a light-emitting element, a blue-emitting light-emitting element exhibiting high color purity can be obtained.
因為本發明的蒽衍生物具有高發光效率,所以具有高發光效率的發光元件可藉由在發光元件中使用本發明的蒽衍生物而獲得。具有高可靠度的發光元件也可藉由在發光元件中使用本發明的蒽衍生物而獲得。 Since the anthracene derivative of the present invention has high luminous efficiency, a light-emitting element having high luminous efficiency can be obtained by using the anthracene derivative of the present invention in a light-emitting element. A light-emitting element having high reliability can also be obtained by using the anthracene derivative of the present invention in a light-emitting element.
因為使用本發明的蒽衍生物之發光元件能夠發出具有高色彩純度的藍光,所以可有利地用於全彩顯示器。再者,使用本發明的蒽衍生物之發光元件達成發出具有高可靠度的藍光之能力允許其在全彩顯示器中的應用。 Since the light-emitting element using the anthracene derivative of the present invention can emit blue light having high color purity, it can be advantageously used for a full-color display. Furthermore, the use of the luminescent element of the hydrazine derivative of the present invention to achieve the ability to emit blue light with high reliability allows its use in full color displays.
應注意在具體實施例模式2中所示之結構可於適當時被使用,除了第三層105之外。 It should be noted that the structure shown in the specific embodiment mode 2 can be used as appropriate, except for the third layer 105.
具有不同於該等在具體實施例模式3及4中所示者之結構的發光元件被敘述於此具體實施例模式中。 A light-emitting element having a structure different from that shown in the specific embodiment modes 3 and 4 is described in this embodiment mode.
所形成之具體實施例模式3中所示之第三層105具有其中發光物質被分散在本發明的蒽衍生物中的結構,藉此可獲得來自發光物質之發光。 The third layer 105 shown in the specific embodiment mode 3 formed has a structure in which a luminescent substance is dispersed in the hydrazine derivative of the present invention, whereby luminescence from the luminescent substance can be obtained.
在其中本發明的蒽衍生物被用作分散另一發光物質之材料的例子中,可獲得自發光物質所得之發光色。再者,也可獲得自本發明的蒽衍生物及分散在蒽衍生物中的發光物質所得之混合發光。 In the example in which the anthracene derivative of the present invention is used as a material for dispersing another luminescent material, the luminescent color obtained from the luminescent material can be obtained. Further, mixed luminescence obtained from the anthracene derivative of the present invention and the luminescent material dispersed in the anthracene derivative can also be obtained.
在此,具有帶間隙比本發明的蒽衍生物更小的物質較佳地被用作被分散在本發明的蒽衍生物中的發光物質。尤其可提供下列物質,如N,N’-雙〔4-(9H-咔唑-9-基)苯 基〕-N,N’-二苯基茋-4,4’-二胺(縮寫:YGA2S)、2,5,8,11-四(第三丁基)苝(縮寫:TBP)、苝、香豆素30、香豆素6、香豆素545T、N,N’-二甲基喹吖啶酮(縮寫:DMQd)、N,N’-二苯基喹吖啶酮(縮寫:DPQd)、N,N,9-三苯基蒽-9-胺(縮寫:DPhAPhA)、5,12-雙(1,1’-聯苯-4-基)-6,11-二苯基四環素(縮寫:BPT)、紅螢烯、N,N,N’,N’-肆(4-甲苯基)四環素-5,11-二胺(縮寫:p-mPhTD)或7,13-二苯基-N,N,N’,N’-肆(4-甲苯基)苊並〔1,2-a〕螢蒽-3,10-二胺(縮寫:p-mPhAFD)。 Here, a substance having a band gap smaller than that of the anthracene derivative of the present invention is preferably used as a luminescent substance dispersed in the anthracene derivative of the present invention. In particular, the following materials can be provided, such as N,N'-bis[4-(9H-carbazol-9-yl)benzene -N,N'-diphenylindole-4,4'-diamine (abbreviation: YGA2S), 2,5,8,11-tetra(t-butyl)anthracene (abbreviation: TBP), hydrazine, Coumarin 30, coumarin 6, coumarin 545T, N, N'-dimethyl quinacridone (abbreviation: DMQd), N, N'-diphenylquinacridone (abbreviation: DPQd) , N,N,9-triphenylphosphonium-9-amine (abbreviation: DPhAPhA), 5,12-bis(1,1'-biphenyl-4-yl)-6,11-diphenyltetracycline (abbreviation :BPT), erythritol, N,N,N',N'-indole (4-methylphenyl)tetracycline-5,11-diamine (abbreviation: p-mPhTD) or 7,13-diphenyl-N , N, N', N'-肆(4-methylphenyl)indeno[1,2-a]fluorescein-3,10-diamine (abbreviation: p-mPhAFD).
因為本發明的蒽衍生物具有大的帶間隙,所以分散在本發明的蒽衍生物中的發光物質係選自寬廣的選擇範圍。例如,可分散展現具有高色彩純度的發藍光之發光物質。尤其,具有大於或等於2.7eV及小於或等於3.0eV之帶間隙的發光物質或具有介於400與500奈米之間的最大發光波長的發光物質被分散在本發明的蒽衍生物中,因為該發光物質展現具有高色彩純度的發藍光,藉此可獲得展現具有高色彩純度的發藍光之發光元件。 Since the anthracene derivative of the present invention has a large band gap, the luminescent substance dispersed in the anthracene derivative of the present invention is selected from a wide range of selection. For example, a blue-emitting luminescent substance having high color purity can be dispersedly exhibited. In particular, a luminescent substance having a band gap of 2.7 eV or more and 3.0 eV or less or a luminescent substance having a maximum luminescent wavelength of between 400 and 500 nm is dispersed in the hydrazine derivative of the present invention because The luminescent substance exhibits blue light having high color purity, whereby a blue light-emitting element exhibiting high color purity can be obtained.
應注意在具體實施例模式3中所示之結構可於適當時被使用,除了第三層105之外。 It should be noted that the structure shown in the specific embodiment mode 3 can be used as appropriate, except for the third layer 105.
具有不同於該等在具體實施例模式3至5中所示者之結構的發光元件被敘述於此具體實施例模式中。 Light-emitting elements having a structure different from those shown in the specific embodiment modes 3 to 5 are described in this embodiment mode.
藉由組合本發明的蒽衍生物與具有關於本發明的蒽衍 生物之電子接受性質的無機化合物,可使含有本發明的蒽衍生物之層用於陽極與發光層之間。尤其含有蒽衍生物之層可用於具體實施例模式3中所示之第一層103或第二層104。載子密度係藉由使用該等複合材料而增加,其有助於改善電洞注射係質及電洞傳輸性質。在複合材料用於第一層103的例子中,第一層103也可達成與第一個電極102的歐姆接觸;因此,第一個電極材料的選擇可無關於功函數。 By combining the anthracene derivatives of the invention with the derivatives of the invention The inorganic compound of the electron accepting property of the living body can be used for the layer containing the anthracene derivative of the present invention between the anode and the light-emitting layer. A layer containing especially an anthracene derivative can be used for the first layer 103 or the second layer 104 shown in the embodiment mode 3. The carrier density is increased by the use of such composite materials, which contributes to improved hole injection system and hole transport properties. In the example where the composite is used for the first layer 103, the first layer 103 can also achieve ohmic contact with the first electrode 102; therefore, the selection of the first electrode material can be independent of the work function.
較佳地使用過渡金屬之氧化物作為用於複合材料的無機化合物。而且,可使用屬於在週期表中的第4至8族之金屬的氧化物。尤其,較佳的是使用氧化釩、氧化鈮、氧化鉭、氧化鉻、氧化鉬、氧化鎢、氧化錳及氧化銠,因為彼等高的電子接受性質。在彼等之中,以氧化鉬特別佳,因為其在空氣下穩定,具有低吸濕性質及容易處理。 An oxide of a transition metal is preferably used as the inorganic compound for the composite material. Moreover, oxides of metals belonging to Groups 4 to 8 in the periodic table can be used. In particular, it is preferred to use vanadium oxide, cerium oxide, cerium oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide and cerium oxide because of their high electron accepting properties. Among them, molybdenum oxide is particularly preferred because it is stable under air, has low hygroscopic properties and is easy to handle.
應注意此具體實施例模式可於適當時與任何其他具體實施例模式組合。 It should be noted that this particular embodiment mode can be combined with any other specific embodiment mode as appropriate.
其中根據本發明的數個發光單元被堆疊的發光元件(以下被稱為堆疊型元件)以參考圖3被敘述於此具體實施例模式中。該發光元件為具有數個介於第一個電極與第二個電極之間的發光單元之堆疊型發光元件。類似於該等在具體實施例模式3至6中所述者之結構被用於每一發光單元中。換言之,在具體實施例模式3中所述之發光元件 為具有一個發光單元之發光元件。具有數個發光單元之發光元件被敘述於此具體實施例模式中。 A light-emitting element in which a plurality of light-emitting units according to the present invention are stacked (hereinafter referred to as a stacked-type element) is described in this embodiment mode with reference to FIG. The light-emitting element is a stacked light-emitting element having a plurality of light-emitting units interposed between the first electrode and the second electrode. Structures similar to those described in the specific embodiment modes 3 to 6 are used in each of the light-emitting units. In other words, the light-emitting element described in the specific embodiment mode 3 It is a light-emitting element having one light-emitting unit. A light-emitting element having a plurality of light-emitting units is described in this embodiment mode.
在圖3中,第一個發光單元511及第二個發光單元512被堆疊在第一個電極501與第二個電極502之間。類似於具體實施例模式2中所述者之電極可應於第一個電極501及第二個電極502。第一個發光單元511及第二個發光單元512可具有相同的結構或不同的結構,並可應用類似於該等在具體實施例模式3至6中所述者之結構。 In FIG. 3, the first light emitting unit 511 and the second light emitting unit 512 are stacked between the first electrode 501 and the second electrode 502. An electrode similar to that described in the embodiment mode 2 can be applied to the first electrode 501 and the second electrode 502. The first light emitting unit 511 and the second light emitting unit 512 may have the same structure or different structures, and may be applied similarly to the structures described in the specific embodiment modes 3 to 6.
電荷產生層513包括有機化合物與金屬氧化物之複合材料。有機化合物與金屬氧化物之複合材料被敘述於具體實施例模式2或5中,並包括有機化合物及金屬氧化物,如氧化釩、氧化鉬或氧化鎢。可使用各種化合物作為有機化合物,如芳香族胺化合物、咔唑衍生物、芳香族烴及高分子化合物(如寡聚物、樹枝狀聚合物或聚合物)。具有大於或等於10-6平方公分/伏特秒之電洞遷移率的有機化合物較佳地被應用為具有電洞傳輸性質的有機化合物。然而,也可使用除了該等化合物之外的其他物質,只要其電洞傳輸性質大於其電子傳輸性質即可。有機化合物與金屬氧化物之複合材料具有卓越的載子注射性質及載子傳輸性質,並因此可實現低電壓驅動及低電流驅動。 The charge generating layer 513 includes a composite material of an organic compound and a metal oxide. The composite of the organic compound and the metal oxide is described in the specific embodiment mode 2 or 5, and includes an organic compound and a metal oxide such as vanadium oxide, molybdenum oxide or tungsten oxide. Various compounds can be used as the organic compound such as an aromatic amine compound, a carbazole derivative, an aromatic hydrocarbon, and a polymer compound such as an oligomer, a dendrimer or a polymer. The organic compound having a hole mobility of greater than or equal to 10 -6 cm 2 /volt second is preferably applied as an organic compound having hole transport properties. However, other substances than the compounds may be used as long as their hole transport properties are greater than their electron transport properties. The composite of organic compound and metal oxide has excellent carrier injection properties and carrier transport properties, and thus can achieve low voltage driving and low current driving.
應注意電荷產生層513可以有機化合物與金屬氧化物之複合材料與其他物質之組合所形成。例如,電荷產生層513可以含有有機化合物與金屬氧化物之複合材料的層與含有一種選自供電子物質之化合物及具有高電子傳輸性質 之化合物的層之組合所形成。再者,電荷產生層513可以含有有機化合物與金屬氧化物之複合材料的層與透明的導電膜之組合所形成。 It should be noted that the charge generating layer 513 can be formed by a combination of a composite of an organic compound and a metal oxide with other substances. For example, the charge generating layer 513 may contain a layer of a composite material of an organic compound and a metal oxide and a compound containing one selected from an electron-donating substance and have high electron transport properties. A combination of layers of the compound is formed. Further, the charge generating layer 513 may be formed by a combination of a layer of a composite material of an organic compound and a metal oxide and a transparent conductive film.
在任何例子中,插置於第一個發光單元511與第二個發光單元512之間的電荷產生層513是可接受的,只要在電壓施予第一個電極501與第二個電極502之間時,電子被注射至一個發光單元中及電洞被注射至其他發光單元中即可。例如,在施予電壓使得第一個電極的電位高於第二個電極的電位的例子中,任何結構之電荷產生層513是可接受的,只要層513注射電子及電洞分別至第一個發光單元511及第二個發光單元512中即可。 In any example, the charge generating layer 513 interposed between the first light emitting unit 511 and the second light emitting unit 512 is acceptable as long as the voltage is applied to the first electrode 501 and the second electrode 502. In the meantime, electrons are injected into one light-emitting unit and holes are injected into other light-emitting units. For example, in the example where the voltage is applied such that the potential of the first electrode is higher than the potential of the second electrode, the charge generating layer 513 of any structure is acceptable as long as the layer 513 injects electrons and holes to the first one, respectively. The light emitting unit 511 and the second light emitting unit 512 may be used.
具有兩種發光單元之發光元件被敘述於此具體實施例模式中;然而,本發明可應用於其中三或多個發光單元被堆疊的發光元件。藉由數個發光單元排列在一對電極之間的方式,使得數個發光單元以電荷產生層分隔,成為此具體實施例模式的發光元件,可以維持低電流密度而實現在高發光區中具有長壽命的元件。在發光元件應用於照明系統的例子中,由於抵抗電極材料的電壓降可降低;因此,在大面積內的均勻發光是可能的。再者,低電壓驅動是可能的,並可實現具有低電力消耗的發光裝置。 A light-emitting element having two kinds of light-emitting units is described in this embodiment mode; however, the present invention is applicable to a light-emitting element in which three or more light-emitting units are stacked. By arranging a plurality of light-emitting units between a pair of electrodes, a plurality of light-emitting units are separated by a charge generating layer, and the light-emitting element of this embodiment mode can maintain a low current density to achieve a high light-emitting area. Long-life components. In the case where the light-emitting element is applied to an illumination system, since the voltage drop against the electrode material can be lowered; therefore, uniform light emission over a large area is possible. Furthermore, low voltage driving is possible, and a light emitting device with low power consumption can be realized.
此具體實施例模式可於適當時與任何其他具體實施例模式組合。 This particular embodiment mode can be combined with any other specific embodiment mode as appropriate.
使用本發明的蒽衍生物所製造的發光裝置被敘述於此具體實施例模式中。 A light-emitting device manufactured using the anthracene derivative of the present invention is described in this specific embodiment mode.
使用本發明的蒽衍生物所製造的發光裝置以參考圖4A及4B被敘述於此具體實施例模式中。圖4A為顯示發光裝置的頂視圖及圖4B為沿著線A-A’及B-B’取得的圖4A之橫截面圖。驅動電路部位(源驅動電路)、像素部位及驅動電路部位(閘驅動電路)分別以參考號碼601、602及603代表,並以虛線表示。密封基板及密封材料也分別以參考號碼604及605代表,並以密封材料605圍繞的部位對應於空間607。 A light-emitting device manufactured using the anthracene derivative of the present invention is described in this embodiment mode with reference to Figs. 4A and 4B. 4A is a top view showing the light-emitting device and FIG. 4B is a cross-sectional view of FIG. 4A taken along lines A-A' and B-B'. The drive circuit portion (source drive circuit), the pixel portion, and the drive circuit portion (gate drive circuit) are represented by reference numerals 601, 602, and 603, respectively, and are indicated by broken lines. The sealing substrate and the sealing material are also represented by reference numerals 604 and 605, respectively, and the portion surrounded by the sealing material 605 corresponds to the space 607.
引導線路608為傳送輸入之訊號至源驅動電路601及閘驅動電路603之線路,並且該線路608接收視訊訊號、時脈訊號、起始訊號、重設訊號及來自外輸入終端的FPC(軟性印刷電路板)609的類似訊號。應注意在此只顯示FPC;然而,FPC俱備印刷電路板(PWB)。在本發明說明書中的發光裝置不僅包括發光裝置本身,並也包括與FPC或PWB連接的發光裝置。 The guiding line 608 is a line for transmitting the input signal to the source driving circuit 601 and the gate driving circuit 603, and the line 608 receives the video signal, the clock signal, the start signal, the reset signal, and the FPC from the external input terminal (soft printing) Circuit board) 609 similar signal. It should be noted that only the FPC is shown here; however, the FPC is provided with a printed circuit board (PWB). The light-emitting device in the specification of the present invention includes not only the light-emitting device itself but also a light-emitting device connected to the FPC or PWB.
接著,橫截面結構以參考圖4B被敘述。驅動電路部位及像素部位形成於元件基板610上。在此顯示源驅動電路601(其為驅動電路部位)及在像素部位602中的一個像素。 Next, the cross-sectional structure is described with reference to FIG. 4B. The driver circuit portion and the pixel portion are formed on the element substrate 610. The source drive circuit 601 (which is the drive circuit portion) and one pixel in the pixel portion 602 are shown here.
CMOS電路(其為n-通道TFT 623與p-通道TFT 624之組合)形成為源驅動電路601。驅動電路可使用各種CMOS電路、PMOS電路或NMOS電路所形成。雖然其中 驅動電路形成於基板上的驅動整合型裝置被敘述於此具體實施例模式中,但是驅動電路沒必要形成於基板上,而可形成為基板之外。 A CMOS circuit, which is a combination of the n-channel TFT 623 and the p-channel TFT 624, is formed as a source driving circuit 601. The drive circuit can be formed using various CMOS circuits, PMOS circuits, or NMOS circuits. Although The drive integrated type device in which the drive circuit is formed on the substrate is described in this embodiment mode, but the drive circuit is not necessarily formed on the substrate but may be formed outside the substrate.
像素部位602具有數個像素,每一像素包括開關TFT 611、電流控制TFT 612及與電流控制TFT 612管子以電連結的第一個電極613。應注意所形成絕緣體614得以覆蓋第一個電極613的末端部位。在此,正型光敏感性丙烯酸樹脂膜被用於絕緣體614。 The pixel portion 602 has a plurality of pixels, and each of the pixels includes a switching TFT 611, a current controlling TFT 612, and a first electrode 613 electrically connected to the current controlling TFT 612 tube. It should be noted that the formed insulator 614 covers the end portion of the first electrode 613. Here, a positive type photosensitive acryl film is used for the insulator 614.
所形成絕緣體614得以形成曲面,在其上末端部位或下末端部位具有曲率,以便獲得有利的覆蓋。例如,在使用正型光敏感性丙烯酸樹脂作為用於絕緣體614之材料的例子中,較佳形成只在上末端部位具有曲率半徑(0.2微米至3微米)的曲面之絕緣體614。以光照射而成為不溶於蝕刻劑中的負型樹脂或以光照射而成為溶於蝕刻劑中的正型樹脂可用於絕緣體614。 The formed insulator 614 is formed into a curved surface having a curvature at its upper end portion or lower end portion in order to obtain favorable coverage. For example, in the case of using a positive type photosensitive acrylic resin as a material for the insulator 614, it is preferable to form an insulator 614 having a curved surface having a radius of curvature (0.2 μm to 3 μm) only at the upper end portion. A negative type resin which is insoluble in an etchant by light irradiation or a positive type resin which is dissolved in an etchant by light irradiation can be used for the insulator 614.
EL層616及第二個電極617形成於第一個電極613上。在此,具有功函數的材料較佳地被用作充當陽極的第一個電極613之材料。例如,第一個電極613可藉由使用氮化鈦膜與含有鋁作為其主要組份的膜之堆疊層;氮化鈦膜、含有鋁作為其主要組份的膜與氮化鈦膜之三層結構;或類似物,及單層膜,如ITO膜、含有矽之氧化銦錫膜、含有2至20重量%之氧化鋅的氧化銦膜、氮化鈦膜、鉻膜、鎢膜、Zn膜或Pt膜所形成。當第一個電極613具有堆疊結構時,該電極613顯示足以充當線路的低電阻,得 到有利的歐姆接觸。 The EL layer 616 and the second electrode 617 are formed on the first electrode 613. Here, a material having a work function is preferably used as a material of the first electrode 613 serving as an anode. For example, the first electrode 613 can be formed by using a titanium nitride film and a stacked layer of a film containing aluminum as its main component; a titanium nitride film, a film containing aluminum as its main component, and a titanium nitride film. Layer structure; or the like, and a single layer film, such as an ITO film, an indium tin oxide film containing antimony, an indium oxide film containing 2 to 20% by weight of zinc oxide, a titanium nitride film, a chromium film, a tungsten film, Zn Formed by a film or a Pt film. When the first electrode 613 has a stacked structure, the electrode 613 exhibits a low resistance enough to function as a line. To a favorable ohmic contact.
另外,EL層616係藉由各種方法所形成,如使用蒸氣罩的蒸發法、噴墨法及旋塗法。EL層616包括在具體實施例模式2中所述之本發明的蒽衍生物。再者,EL層616可使用另一種含有低分子化合物或高分子化合物(含有寡聚物及樹枝狀聚合物)的材料而形成。 Further, the EL layer 616 is formed by various methods such as an evaporation method using a vapor hood, an inkjet method, and a spin coating method. The EL layer 616 includes the anthracene derivative of the present invention described in the embodiment mode 2. Further, the EL layer 616 can be formed using another material containing a low molecular compound or a high molecular compound (containing an oligomer and a dendrimer).
較佳地使用具有低功函數之材料(Al、Mg、Li、Ca,或其合金或化合物,如MgAg、MgIn、AlLi、LiF或CaF2)作為形成於EL層616上且充當陰極之用於第二個電極617的材料。在在EL層616中所產生的光經由第二個電極617傳送的例子中,較佳地使用金屬薄膜與透明的導電性膜(ITO,含有2至20重量%之氧化鋅的氧化銦、含有矽或氧化矽之氧化銦-氧化錫、氧化鋅(ZnO)或類似物)之堆疊層作為第二個電極617。 It is preferable to use a material having a low work function (Al, Mg, Li, Ca, or an alloy thereof or a compound such as MgAg, MgIn, AlLi, LiF or CaF 2 ) as being formed on the EL layer 616 and serving as a cathode. The material of the second electrode 617. In the example in which the light generated in the EL layer 616 is transmitted via the second electrode 617, a metal thin film and a transparent conductive film (ITO, indium oxide containing 2 to 20% by weight of zinc oxide, containing A stacked layer of indium oxide-tin oxide, zinc oxide (ZnO) or the like of cerium oxide or cerium oxide is used as the second electrode 617.
藉由以密封材料605連接密封基板604與元件基板610,使得在具體實施例模式3至7中所示之本發明的發光元件618被使用於以元件基板610、密封基板604及密封材料605所圍繞的空間607中。應注意惰性氣體(氮、氬或類似物)填充空間607。也有以密封材料605填充空間607的例子。 By connecting the sealing substrate 604 and the element substrate 610 with the sealing material 605, the light-emitting elements 618 of the present invention shown in the specific embodiment modes 3 to 7 are used for the element substrate 610, the sealing substrate 604, and the sealing material 605. Surrounded by space 607. It should be noted that an inert gas (nitrogen, argon or the like) fills the space 607. There is also an example in which the space 607 is filled with the sealing material 605.
應注意以環氧樹脂為主之樹脂較佳地被用作密封材料605。希望該材料允許儘可能少量的濕氣及氧氣穿透。可使用由FRP(纖維玻璃強化之塑膠)、PVF(聚氟乙烯)、聚酯、丙烯酸樹脂或類似物形成的塑膠基板與玻璃 基板或石英基板作為密封基板604。 It should be noted that an epoxy resin-based resin is preferably used as the sealing material 605. It is expected that the material will allow as little moisture and oxygen penetration as possible. A plastic substrate and glass formed of FRP (fiber glass reinforced plastic), PVF (polyvinyl fluoride), polyester, acrylic resin or the like can be used. A substrate or a quartz substrate is used as the sealing substrate 604.
如上所述,可獲得含有本發明的蒽衍生物之發光裝置。 As described above, a light-emitting device containing the anthracene derivative of the present invention can be obtained.
因為在具體實施例模式2中所述之蒽衍生物被用於本發明的發光裝置,所以可獲得具有高性能的發光裝置。尤其可獲得具有長壽命的發光裝置。 Since the anthracene derivative described in the specific embodiment mode 2 is used for the light-emitting device of the present invention, a light-emitting device having high performance can be obtained. In particular, a light-emitting device having a long life can be obtained.
也因為本發明的蒽衍生物具有高發光效率,所以可獲得具有低電力消耗的發光裝置。 Also, since the anthracene derivative of the present invention has high luminous efficiency, a light-emitting device having low power consumption can be obtained.
再者,因為本發明的蒽衍生物能夠發出具有高色彩純度的藍光,所以蒽衍生物可有利地用於全彩顯示器。再者,因為本發明的蒽衍生物能夠發出具有高可靠度及低電力消耗的藍光,所以其可有利地用於全彩顯示器。 Furthermore, since the anthracene derivative of the present invention is capable of emitting blue light having high color purity, the anthracene derivative can be advantageously used for a full color display. Furthermore, since the anthracene derivative of the present invention can emit blue light having high reliability and low power consumption, it can be advantageously used for a full color display.
再者,本發明的蒽衍生物能夠發出具有高色彩純度的藍光,所以可獲得具有高色彩再現性的發光裝置。 Further, the anthracene derivative of the present invention can emit blue light having high color purity, so that a light-emitting device having high color reproducibility can be obtained.
如上所述,控制具有電晶體之發光元件的主動式矩陣發光裝置被敘述於此具體實施例模式中;然而,可使用被動式矩陣發光裝置。應用本發明所製造的被動式矩陣發光裝置之透視圖顯示在圖5A中。圖5A為發光裝置的透視圖及圖5B為沿著線X-Y所得的圖5A之橫截面圖。在圖5A及5B中,EL層955被使用在基板951上介於電極952與電極956之間。電極952的末端以絕緣層953覆蓋。接著分隔層954被使用在絕緣層953上。分隔層954的側壁傾斜,使得一個側壁與其他側壁之間的距離朝向基板表面變窄。換言之,在短邊方向上的分隔層954橫截面 為梯形,並且底部(在類似於絕緣層953的平面方向的方向上延伸且與絕緣層953接觸的一邊)比上邊(在類似於絕緣層953的平面方向的方向上延伸且不與絕緣層953接觸的一邊)更短。以該方式所提供的分隔層954可避免發光元件由於靜電所產生的缺陷。在被動式矩陣發光裝置的例子中,具有高可靠度及長壽命的發光裝置也可藉由使用本發明的蒽衍生物而獲得。再者,可獲得具有低電力消耗的發光裝置。 As described above, an active matrix light-emitting device that controls a light-emitting element having a transistor is described in this embodiment mode; however, a passive matrix light-emitting device can be used. A perspective view of a passive matrix illumination device fabricated using the present invention is shown in Figure 5A. 5A is a perspective view of the light emitting device and FIG. 5B is a cross-sectional view of FIG. 5A taken along line X-Y. In FIGS. 5A and 5B, an EL layer 955 is used on the substrate 951 between the electrode 952 and the electrode 956. The end of the electrode 952 is covered with an insulating layer 953. A spacer layer 954 is then used on the insulating layer 953. The side walls of the spacer layer 954 are inclined such that the distance between one side wall and the other side walls is narrowed toward the surface of the substrate. In other words, the cross section of the spacer layer 954 in the short side direction It is trapezoidal, and the bottom (the side extending in the direction similar to the planar direction of the insulating layer 953 and in contact with the insulating layer 953) is longer than the upper side (in the direction similar to the planar direction of the insulating layer 953 and not with the insulating layer 953) The side of the contact) is shorter. The spacer layer 954 provided in this manner can avoid defects of the light-emitting element due to static electricity. In the example of the passive matrix light-emitting device, a light-emitting device having high reliability and long life can also be obtained by using the anthracene derivative of the present invention. Furthermore, a light-emitting device with low power consumption can be obtained.
部分含有在具體實施例模式8中所述之發光裝置的本發明的電子裝置被敘述在此具體實施例模式中。本發明的電子裝置包括在具體實施例模式2中所述之蒽衍生物,並具有高可靠度及長壽命的顯示部位。本發明的電子裝置也具有低電力消耗的顯示部位。 The electronic device of the present invention partially containing the light-emitting device described in Embodiment Mode 8 is described in this embodiment mode. The electronic device of the present invention comprises the anthracene derivative described in Embodiment Mode 2, and has a display portion of high reliability and long life. The electronic device of the present invention also has a display portion with low power consumption.
提供照相機,如攝影機或數位照相機、眼鏡型顯示器、導航系統、視聽再現裝置(汽車立體音響組合、立體音響組合或類似物)、電腦、遊戲機、可攜式信息終端機(手攜式電腦、行動電話、可攜式遊戲機、電子書或類似物)及俱備記錄媒介的影像再現裝置(尤其能夠再顯記錄媒介之裝置,如數位多功能光碟(DVD),且俱備可顯示影像的顯示器裝置之裝置)及類似物作為使用本發明的蒽衍生物所製造之含有發光元件的電子裝置。該等電子裝置的特殊實例顯示在圖6A至6D。 Providing cameras such as video cameras or digital cameras, glasses-type displays, navigation systems, audio-visual reproduction devices (automotive stereo combinations, stereo combinations or the like), computers, game consoles, portable information terminals (handheld computers, Mobile phone, portable game console, e-book or the like) and an image reproduction device for recording media (especially a device capable of re-displaying a recording medium such as a digital versatile disc (DVD), and all of which can display images. An apparatus for a display device and the like as an electronic device including a light-emitting element manufactured using the anthracene derivative of the present invention. Specific examples of such electronic devices are shown in Figures 6A through 6D.
圖6A顯示根據本發明的電視裝置,其包括框架9101、支撐座9102、顯示部位9103、喇叭部位9104、視訊輸入終端9105及類似物。在電視裝置中,顯示部位9103具有類似於該等在具體實施例模式3至7中所述之發光元件,並將發光元件以矩陣排列。發光元件的特點係以高發光效率及長壽命舉例說明。含有發光元件的顯示部位9103具有類似的特點。因此,在電視裝置中,影像品質決不會惡化且達成低電力消耗。由於該等特點,可使惡化補償功能及電力供應電路顯著地減少或使在電視裝置中的尺寸縮減,其能夠縮減框架9101及支撐座9102的尺寸及重量。在根據本發明的電視裝置中,達成低電力消耗、高影像品質及小尺寸與輕重量;因此,可提供適合於生活環境的產品。也因為在具體實施例模式1中所述之蒽衍生物能夠具有高色彩純度的發藍光,所以全彩顯示器是可能的,並可獲得具有高色彩再現性之顯示部位的電視裝置。 再者,可獲得具有長壽命之顯示部位的電視裝置。 6A shows a television device according to the present invention including a frame 9101, a support base 9102, a display portion 9103, a horn portion 9104, a video input terminal 9105, and the like. In the television device, the display portion 9103 has light-emitting elements similar to those described in the specific embodiment modes 3 to 7, and the light-emitting elements are arranged in a matrix. The characteristics of the light-emitting element are exemplified by high luminous efficiency and long life. The display portion 9103 containing the light-emitting elements has similar features. Therefore, in the television device, the image quality is never deteriorated and low power consumption is achieved. Due to these characteristics, the deterioration compensation function and the power supply circuit can be significantly reduced or the size in the television device can be reduced, which can reduce the size and weight of the frame 9101 and the support base 9102. In the television device according to the present invention, low power consumption, high image quality, and small size and light weight are achieved; therefore, a product suitable for a living environment can be provided. Also, since the anthracene derivative described in the embodiment mode 1 can have a blue light of high color purity, a full color display is possible, and a television device having a display portion with high color reproducibility can be obtained. Furthermore, a television device having a display portion having a long life can be obtained.
圖6B顯示根據本發明的電腦,其包括主體9201、框架9202、顯示部位9203、鍵盤9204、外連結口9205、指向裝置9206及類似物。在電腦中,顯示部位9203具有類似於該等在具體實施例模式3至7中所述之發光元件,並將發光元件以矩陣排列。發光元件的特點係以高發光效率及長壽命舉例說明。含有發光元件的顯示部位9203具有類似的特點。因此,在電腦中,影像品質決不會惡化且達成較低的電力消耗。由於該等特點,可使惡化補償功能及 電力供應電路顯著地減少或使在電腦中的尺寸縮減;因此,可達成小尺寸及輕重量的主體9201及框架9202。在根據本發明的電腦中,達成低電力消耗、高影像品質及小尺寸與輕重量;因此,可供應適合於環境的產品。再者,因為在具體實施例模式1中所述之蒽衍生物能夠具有高色彩純度的發藍光,所以全彩顯示器是可能的,並可獲得具有高色彩再現性之顯示部位的電腦。再者,可獲得具有長壽命之顯示部位的電腦。 6B shows a computer according to the present invention including a main body 9201, a frame 9202, a display portion 9203, a keyboard 9204, an external connection port 9205, a pointing device 9206, and the like. In the computer, the display portion 9203 has light-emitting elements similar to those described in the specific embodiment modes 3 to 7, and the light-emitting elements are arranged in a matrix. The characteristics of the light-emitting element are exemplified by high luminous efficiency and long life. The display portion 9203 containing the light-emitting elements has similar features. Therefore, in a computer, image quality never deteriorates and lower power consumption is achieved. Due to these characteristics, the deterioration compensation function and The power supply circuit significantly reduces or reduces the size in the computer; therefore, the small size and light weight of the main body 9201 and the frame 9202 can be achieved. In the computer according to the present invention, low power consumption, high image quality, and small size and light weight are achieved; therefore, products suitable for the environment can be supplied. Further, since the anthracene derivative described in Embodiment Mode 1 can have a blue light of high color purity, a full color display is possible, and a computer having a display portion with high color reproducibility can be obtained. Furthermore, a computer having a long-life display portion can be obtained.
圖6C顯示根據本發明的行動電話,其包括主體9401、框架9402、顯示部位9403、視訊輸入部位9404、視訊輸出部位9405、操作鍵9406、外連結口9407、天線9408及類似物。在行動電話中,顯示部位9403具有類似於該等在具體實施例模式3至7中所述之發光元件,並將發光元件以矩陣排列。發光元件的特點係以高發光效率及長壽命舉例說明。含有發光元件的顯示部位9403具有類似的特點。因此,在行動電話中,影像品質決不會惡化且達成較低的電力消耗。由於該等特點,可使惡化補償功能及電力供應電路顯著地減少或使在行動電話中的尺寸縮減;因此,可達成小尺寸及輕重量的主體9401及框架9402。在根據本發明的行動電話中,達成低電力消耗、高影像品質及小尺寸與輕重量;因此,可提供適合攜帶的產品。再者,因為在具體實施例模式1中所述之蒽衍生物能夠具有高色彩純度的發藍光,所以全彩顯示器是可能的,並可獲得具有高色彩再現性之顯示部位的行動電話。再 者,可獲得具有長壽命之顯示部位的行動電話。 6C shows a mobile phone according to the present invention, which includes a main body 9401, a frame 9402, a display portion 9403, a video input portion 9404, a video output portion 9405, operation keys 9406, an external connection port 9407, an antenna 9408, and the like. In the mobile phone, the display portion 9403 has light-emitting elements similar to those described in the specific embodiment modes 3 to 7, and the light-emitting elements are arranged in a matrix. The characteristics of the light-emitting element are exemplified by high luminous efficiency and long life. The display portion 9403 containing the light-emitting elements has similar features. Therefore, in mobile phones, image quality never deteriorates and lower power consumption is achieved. Due to these characteristics, the deterioration compensation function and the power supply circuit can be remarkably reduced or the size in the mobile phone can be reduced; therefore, the small size and light weight of the main body 9401 and the frame 9402 can be achieved. In the mobile phone according to the present invention, low power consumption, high image quality, and small size and light weight are achieved; therefore, a product suitable for carrying can be provided. Further, since the anthracene derivative described in Embodiment Mode 1 can have a blue light of high color purity, a full color display is possible, and a mobile phone having a display portion with high color reproducibility can be obtained. again A mobile phone having a long-life display portion can be obtained.
圖6D顯示根據本發明的照相機,其包括主體9501、顯示部位9502、框架9503、外連結口9504、遠端控制接收部位9505、影像接受部位9506、電池9507、視訊輸入部位9508、操作鍵9509、目鏡部位9510及類似物。在照相機中,顯示部位9502具有類似於該等在具體實施例模式3至7中所述之發光元件,並將發光元件以矩陣排列。發光元件的特點係以高發光效率及長壽命舉例說明。含有發光元件的顯示部位9502具有類似的特點。因此,在照相機中,影像品質決不會惡化且可達成較低的電力消耗。由於該等特點,可使惡化補償功能及電力供應電路顯著地減少或使在照相機中的尺寸縮減;因此,可達成小尺寸及輕重量的主體9501。在根據本發明的照相機中,達成低電力消耗、高影像品質及小尺寸與輕重量;因此,可提供適合攜帶的產品。再者,因為在具體實施例模式1中所述之蒽衍生物能夠具有高色彩純度的發藍光,所以全彩顯示器是可能的,並可獲得具有高色彩再現性之顯示部位的照相機。再者,可獲得具有長壽命之顯示部位的照相機。 6D shows a camera according to the present invention, which includes a main body 9501, a display portion 9502, a frame 9503, an external connection port 9504, a remote control receiving portion 9505, an image receiving portion 9506, a battery 9507, a video input portion 9508, an operation key 9509, Eyepiece portion 9510 and the like. In the camera, the display portion 9502 has light-emitting elements similar to those described in the specific embodiment modes 3 to 7, and the light-emitting elements are arranged in a matrix. The characteristics of the light-emitting element are exemplified by high luminous efficiency and long life. The display portion 9502 containing the light-emitting elements has similar features. Therefore, in the camera, the image quality is never deteriorated and a lower power consumption can be achieved. Due to these characteristics, the deterioration compensation function and the power supply circuit can be remarkably reduced or the size in the camera can be reduced; therefore, the small size and light weight of the main body 9501 can be achieved. In the camera according to the present invention, low power consumption, high image quality, and small size and light weight are achieved; therefore, a product suitable for carrying can be provided. Further, since the anthracene derivative described in the embodiment mode 1 can have a blue light of high color purity, a full color display is possible, and a camera having a display portion with high color reproducibility can be obtained. Furthermore, a camera having a long-life display portion can be obtained.
如上所述,本發明的發光裝置的可應用範圍如此寬廣,所以發光裝置可應用於各種領域中的電子裝置。具有長壽命之顯示部位的電子裝置可藉由使用本發明的蒽衍生物而提供。再者,可獲得具有高色彩再現性之顯示部位的電子裝置。 As described above, the applicable range of the light-emitting device of the present invention is so wide that the light-emitting device can be applied to electronic devices in various fields. An electronic device having a long-life display portion can be provided by using the anthracene derivative of the present invention. Furthermore, an electronic device having a display portion with high color reproducibility can be obtained.
本發明的發光裝置也可被用作照明系統。一種使用本 發明的發光元件作為照明系統的模式以參考圖7被敘述。 The illumination device of the present invention can also be used as an illumination system. Use of this The mode of the inventive light-emitting element as an illumination system is described with reference to FIG.
圖7顯示使用本發明的發光裝置作為背光的一液晶顯示器裝置。在圖7中所示之液晶顯示器裝置包括框架901、液晶層902、背光903及框架904,並且液晶層902與驅動IC 905連結。本發明的發光裝置被用於背光903,並且電流係經由接頭906供應。 Fig. 7 shows a liquid crystal display device using the light-emitting device of the present invention as a backlight. The liquid crystal display device shown in FIG. 7 includes a frame 901, a liquid crystal layer 902, a backlight 903, and a frame 904, and the liquid crystal layer 902 is coupled to the driving IC 905. The light emitting device of the present invention is used for the backlight 903, and the current is supplied via the joint 906.
具有減少電力消耗及高發光效率之背光可藉由使用本發明的發光裝置作為液晶顯示器裝置的背光而獲得。本發明的發光裝置為具有平面發光之照明系統,並可具有大面積。因此,背光可具有大面積,並可獲得具有大面積的液晶顯示器裝置。此外,本發明的發光裝置具有薄形狀及具有低電力消耗;因此也可達成薄形狀及低電力消耗的顯示器裝置。因為本發明的發光裝置具有長壽命,所以使用本發明的發光裝置之液晶顯示器裝置也具有長壽命。 A backlight having reduced power consumption and high luminous efficiency can be obtained by using the light-emitting device of the present invention as a backlight of a liquid crystal display device. The light-emitting device of the present invention is an illumination system having planar illumination and can have a large area. Therefore, the backlight can have a large area, and a liquid crystal display device having a large area can be obtained. Further, the light-emitting device of the present invention has a thin shape and low power consumption; therefore, a display device having a thin shape and low power consumption can be achieved. Since the light-emitting device of the present invention has a long life, the liquid crystal display device using the light-emitting device of the present invention also has a long life.
圖8顯示應用本發明的發光裝置之一實例。在圖8中,說明應用於桌燈作為照明系統的一實例。在圖8中所示之桌燈包括框架2001及光源2002,並且本發明的發光裝置被用作光源2002。本發明的發光裝置具有高發光效率及具有長壽命;因此,桌燈也具有高發光效率及長壽命。 Fig. 8 shows an example of a light-emitting device to which the present invention is applied. In Fig. 8, an example of application to a table lamp as an illumination system is illustrated. The table lamp shown in Fig. 8 includes a frame 2001 and a light source 2002, and the light-emitting device of the present invention is used as the light source 2002. The light-emitting device of the present invention has high luminous efficiency and has a long life; therefore, the table lamp also has high luminous efficiency and long life.
圖9顯示應用本發明的發光裝置之一實例。圖9顯示應用於室內照明系統3001的一實例。因為本發明的發光裝置也具有大面積,所以本發明的發光裝置可被用作具有大發光面積的照明系統。再者,本發明的發光裝置具有薄 形狀及消耗低的電力;本發明的發光裝置可被用作具有薄形狀及低電力消耗的照明系統。如在圖6A中所述,根據本發明的電視裝置3002被放置在其中應用本發明的發光裝置被用作室內照明裝置3001的室內,並可觀看公共廣播及電影。在該例子中,因為該兩種裝置消耗低電力,所以有效力的影像可在明亮的室內觀看,而不擔心電費。 Fig. 9 shows an example of a light-emitting device to which the present invention is applied. FIG. 9 shows an example of application to the indoor lighting system 3001. Since the light-emitting device of the present invention also has a large area, the light-emitting device of the present invention can be used as an illumination system having a large light-emitting area. Furthermore, the light-emitting device of the present invention has a thin Shape and low power consumption; the light-emitting device of the present invention can be used as an illumination system having a thin shape and low power consumption. As described in FIG. 6A, the television device 3002 according to the present invention is placed in a room in which the light-emitting device to which the present invention is applied is used as the indoor lighting device 3001, and public broadcasting and movies can be viewed. In this example, since the two devices consume low power, the effective image can be viewed in a bright room without worrying about the electricity bill.
以結構式(11)代表的9-〔4-(N-咔唑基)〕苯基-10-苯蒽(縮寫:CzPA)之合成法被敘述於此具體實施例中。 The synthesis of 9-[4-(N-carbazolyl)]phenyl-10-benzoquinone (abbreviation: CzPA) represented by the formula (11) is described in this specific example.
將9-苯蒽的合成流程顯示在(B-1)中。 The synthetic scheme of 9-phenylhydrazine is shown in (B-1).
將25.7公克(100毫莫耳)9-溴蒽、12.8公克(105毫莫耳)苯基硼酸、233毫克(1.0毫莫耳)乙酸鈀(II)及913毫克(3.0毫莫耳)三(鄰-甲苯基)膦放入500毫升三頸燒瓶中,並進行氮取代。接著將100毫升乙二醇二甲醚及75毫升(190毫莫耳)碳酸鈉水溶液(2.0莫耳/公升)加入其中,並將反應混合物在90℃下攪拌5小時。在反應之後,使反應混合物接受抽氣過濾,收集沉澱之固體。將所獲得的固體溶解在甲苯中,並使所得溶液接受經由矽酸鎂(Florisil)、矽藻土及接著氧化鋁的抽氣過濾。將過濾物以水及飽和食鹽水清洗,並接著將有機層以硫酸鎂乾燥。將該混合物自然過濾及將過濾物冷凝,獲得具有98%產率之25.0公克淺棕色固體,其為標的物。 25.7 grams (100 millimoles) of 9-bromoindole, 12.8 grams (105 millimoles) of phenylboronic acid, 233 milligrams (1.0 millimoles) of palladium (II) acetate, and 913 milligrams (3.0 millimoles) of three ( The o-tolylphosphine was placed in a 500 ml three-necked flask and subjected to nitrogen substitution. Next, 100 ml of ethylene glycol dimethyl ether and 75 ml (190 mmol) of an aqueous sodium carbonate solution (2.0 mol/liter) were added thereto, and the reaction mixture was stirred at 90 ° C for 5 hours. After the reaction, the reaction mixture was subjected to suction filtration, and the precipitated solid was collected. The obtained solid was dissolved in toluene, and the resulting solution was subjected to suction filtration through Florisil, diatomaceous earth and then alumina. The filtrate was washed with water and saturated brine, and then the organic layer was dried over magnesium sulfate. The mixture was naturally filtered and the filtrate was condensed to afford 25.0 g of light brown solid, 98% yield, as the subject matter.
將9-溴基-10-苯蒽的合成流程顯示在(B-2)中。 The synthetic scheme of 9-bromo-10-benzoquinone is shown in (B-2).
將25.0公克(98.3毫莫耳)9-苯蒽放入1公升三頸燒瓶中,並將300毫升四氯化碳加入其中。將其中15.6公克(98.3毫莫耳)溴溶解在40毫升四氯化碳中的溶液滴入在室溫下的反應溶液中。在滴完之後,將反應溶液在室溫下攪拌1小時。然後反應係藉由加入硫代硫酸鈉水溶液而完成,並將溶液再攪拌1小時。將反應混合物的有機層以水性氫氧化鈉(2.0莫耳/公升)及飽和食鹽水清洗,並以硫酸鎂乾燥。將該混合物自然過濾及將過濾物冷凝,獲得固體。將固體溶解在甲苯中,並使所得溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物濃縮,獲得固體,並將固體以二氯甲烷與己烷的混合溶液再結晶,藉此獲得具有85%產率之27.8公克淺黃色粉狀固體,其為標的物。 25.0 g (98.3 mmol) of 9-phenylhydrazine was placed in a 1 liter three-necked flask, and 300 ml of carbon tetrachloride was added thereto. A solution in which 15.6 g (98.3 mmol) of bromine was dissolved in 40 ml of carbon tetrachloride was dropped into the reaction solution at room temperature. After the completion of the dropwise addition, the reaction solution was stirred at room temperature for 1 hour. The reaction was then completed by the addition of aqueous sodium thiosulfate solution and the solution was stirred for an additional hour. The organic layer of the reaction mixture was washed with aqueous sodium hydroxide (2.0 m/l) and brine and dried over magnesium sulfate. The mixture was naturally filtered and the filtrate was condensed to give a solid. The solid was dissolved in toluene, and the resulting solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth and then alumina. The filtrate was concentrated to give a solid, and the solid was recrystallized from a mixture of methylene chloride and hexane, whereby 27.8 g of a pale yellow powdery solid having an 85% yield was obtained as the subject matter.
將N-(4-溴苯基)咔唑的合成流程顯示在(B-3)中。 The synthetic scheme of N-(4-bromophenyl)carbazole is shown in (B-3).
將56.3公克(0.24莫耳)1,4-二溴苯、31.3公克 (0.18莫耳)咔唑、4.6公克(0.024莫耳)碘化亞銅(I)、66.3公克(0.48莫耳)碳酸鉀及2.1公克(0.008莫耳)18-冠狀-6-醚放入300毫升三頸燒瓶中,並進行氮取代。接著將8毫升1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮(DMPU)加入其中,並將反應混合物在180℃下攪拌6小時。在反應混合物冷卻至室溫之後,將沉澱物以抽氣過濾移除。將過濾物以稀釋的氫氯酸、碳酸氫鈉飽和水溶液及飽和食鹽水溶液以該次序清洗。將有機層以硫酸鎂乾燥。在乾燥之後,將混合物自然過濾及將過濾物濃縮,獲得油狀物質。將物質以矽膠管柱層析法(己烷:乙酸乙酯=9:1作為顯像溶劑)純化。將所得固體以氯仿與己烷的混合溶劑再結晶,藉此獲得具有35%產率之20.7公克淺棕色薄板狀晶體,其為標的物。 Will be 56.3 grams (0.24 moles) 1,4-dibromobenzene, 31.3 grams (0.18 mol) carbazole, 4.6 g (0.024 mol) cuprous iodide (I), 66.3 g (0.48 mol) potassium carbonate and 2.1 g (0.008 mol) 18-coron-6-ether in 300 Dilute in a three-necked flask and replace with nitrogen. Next, 8 ml of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) was added thereto, and the reaction mixture was stirred at 180 ° C for 6 hours. After the reaction mixture was cooled to room temperature, the precipitate was removed by suction filtration. The filtrate was washed in this order with diluted hydrochloric acid, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of brine. The organic layer was dried over magnesium sulfate. After drying, the mixture was naturally filtered and the filtrate was concentrated to give an oily material. The material was purified by silica gel column chromatography (hexane: ethyl acetate = 9:1). The obtained solid was recrystallized from a mixed solvent of chloroform and hexane, whereby 20.7 g of light brown thin plate crystals having a yield of 35% were obtained, which was the subject matter.
將4-(咔唑-9-基)苯基硼酸的合成流程顯示在(B-4)中。 The synthetic scheme of 4-(carbazol-9-yl)phenylboronic acid is shown in (B-4).
將21.8公克(67.5毫莫耳)N-(4-溴苯基)咔唑放 入500毫升三頸燒瓶中,並進行氮取代。然後加入200毫升四氫呋喃(THF),使反應系統內部維持在-78℃下。將48.9毫升(74.3毫莫耳)正丁基鋰(1.52莫耳/公升己烷溶液)滴入該反應溶液中,並將溶液在相同的溫度下攪拌2小時。加入17.4毫升(155毫莫耳)硼酸三甲酯及將溶液在-78℃下攪拌1小時,並接著將溶液攪拌12小時,同時允許反應溫度逐漸增加至室溫。在反應之後,將200毫升氫氯酸(1莫耳/公升)加入反應溶液中,並將溶液在室溫下攪拌1小時。將反應混合物以水清洗,以乙酸乙酯萃取水層。將萃取之溶液與有機層一起以飽和食鹽水清洗及以硫酸鎂乾燥。在乾燥之後,使混合物接受抽氣過濾及將過濾物冷凝,獲得固體。將固體以氯仿與己烷的混合溶液再結晶,藉此獲得具有66%產率之12.8公克白色粉狀固體,其為標的物。 Place 21.8 grams (67.5 millimoles) of N-(4-bromophenyl)carbazole Into a 500 ml three-necked flask and replace with nitrogen. Then, 200 ml of tetrahydrofuran (THF) was added to maintain the inside of the reaction system at -78 °C. 48.9 ml (74.3 mmol) of n-butyllithium (1.52 mol/liter hexane solution) was dropped into the reaction solution, and the solution was stirred at the same temperature for 2 hours. 17.4 ml (155 mmol) of trimethyl borate was added and the solution was stirred at -78 °C for 1 hour, and then the solution was stirred for 12 hours while allowing the reaction temperature to gradually increase to room temperature. After the reaction, 200 ml of hydrochloric acid (1 mol/liter) was added to the reaction solution, and the solution was stirred at room temperature for 1 hour. The reaction mixture was washed with water and aq. The extracted solution was washed with a saturated brine and dried over magnesium sulfate. After drying, the mixture was subjected to suction filtration and the filtrate was condensed to obtain a solid. The solid was recrystallized from a mixed solution of chloroform and hexane, whereby 12.8 g of a white powdery solid having a yield of 66% was obtained as the subject matter.
將CzPA的合成流程顯示在(B-5)中。 The synthetic scheme of CzPA is shown in (B-5).
將1.44公克(4.32毫莫耳)9-溴基-10-苯蒽、1.49公克(5.19毫莫耳)4-(咔唑-9-基)苯基硼酸咔唑、38.0毫克(0.17毫莫耳)乙酸鈀(II)及0.36公克(1.21毫莫耳)參(鄰-甲苯基)膦放入100毫升三頸燒瓶中,並進行氮取代。接著加入10毫升乙二醇二甲醚(DME)及6.5毫升(13.0毫莫耳)碳酸鈉水溶液(2.0莫耳/公升),並將溶液在90℃下攪拌4小時。然後使反應混合物接受抽氣過濾,收集沉澱之固體。將所獲得的固體溶解在氯仿中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以氯仿與己烷的混合溶劑再結晶,藉此獲得具有85%產率之18.1公克淺黃色粉狀固體,其為標的物。藉由核磁共振測量(NMR)確認該化合物為9-〔4-(N-咔唑基)〕苯基-10-苯蒽(縮寫:CzPA)。 1.44 g (4.32 mmol) of 9-bromo-10-benzoquinone, 1.49 g (5.19 mmol) of 4-(carbazol-9-yl)phenylboronic acid carbazole, 38.0 mg (0.17 mmol) Palladium(II) acetate and 0.36 g (1.21 mmol) of ginseng (o-tolyl)phosphine were placed in a 100 ml three-necked flask and subjected to nitrogen substitution. Next, 10 ml of ethylene glycol dimethyl ether (DME) and 6.5 ml (13.0 mmol) of an aqueous sodium carbonate solution (2.0 mol/liter) were added, and the solution was stirred at 90 ° C for 4 hours. The reaction mixture was then subjected to suction filtration and the precipitated solid was collected. The obtained solid was dissolved in chloroform, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth and then alumina. The filtrate was condensed to obtain a solid, and the solid was recrystallized from a mixed solvent of chloroform and hexane, whereby 18.1 g of a pale yellow powdery solid having an 85% yield was obtained as a target. The compound was confirmed to be 9-[4-(N-carbazolyl)]phenyl-10-benzoquinone (abbreviation: CzPA) by nuclear magnetic resonance measurement (NMR).
CzPA的1H NMR數據顯示於下。1H NMR(300MHz,CDCl3);δ=8.22(d,J=7.8Hz,2H),7.86-7.82(m,3H),7.61-7.36(m,20H)。1H NMR圖顯示於圖10A及10B 中。應注意在圖10A中的6.5ppm至8.5ppm之範圍擴大顯示於圖10B中。 The 1 H NMR data of CzPA is shown below. 1 H NMR (300 MHz, CDCl 3 ); δ = 8.22 (d, J = 7.8 Hz, 2H), 7.86-7.82 (m, 3H), 7.61 - 7.36 (m, 20H). The 1 H NMR chart is shown in Figures 10A and 10B. It should be noted that the range expansion of 6.5 ppm to 8.5 ppm in Fig. 10A is shown in Fig. 10B.
CzPA的熱重分析-微差熱分析(TG-DTA)係使用熱重分析儀/微差熱分析儀(TG/DTA 320,Seiko Instruments Inc.之產品)進行。熱物理性質係在氮氣下以10℃/分鐘的溫度上升速度評估。結果,基於重力與溫度之間的關係(熱重分析測量),在正常壓力下的溫度為348℃,其為重力為95%或更低的測量開始點之重力下的溫度。以示差掃描熱析儀(Pyris 1 DSC,Perkin Elmer Co.,Ltd.之產品)所測量之CzPA的玻璃轉換溫度及熔點分別為125℃及305℃;因此,發現CzPA具有熱穩定性。 Thermogravimetric Analysis of CzPA - Differential Thermal Analysis (TG-DTA) was carried out using a thermogravimetric analyzer/differential thermal analyzer (TG/DTA 320, product of Seiko Instruments Inc.). The thermophysical properties were evaluated under nitrogen at a rate of temperature rise of 10 ° C / min. As a result, based on the relationship between gravity and temperature (measured by thermogravimetric analysis), the temperature under normal pressure was 348 ° C, which is the temperature under the gravity of the measurement starting point of gravity of 95% or less. The glass transition temperature and melting point of CzPA measured by a differential scanning calorimeter (Pyris 1 DSC, product of Perkin Elmer Co., Ltd.) were 125 ° C and 305 ° C, respectively; therefore, CzPA was found to be thermally stable.
圖11顯示CzPA之甲苯溶液的吸收光譜。圖12顯示CzPA之薄膜的吸收光譜。紫外光-可見光分光光度計(V-550,由JASCO Corporation所製造)用於測量。將溶液放入石英槽中及將薄膜樣品在石英基板上蒸發,形成樣品。來自每一減掉石英吸收光譜的其吸收光譜顯示在圖11及12中。在圖11及12中,水平軸表示波長(奈米)及垂直軸表示吸收強度(以單元表示)。在甲苯溶液的例子中,以蒽骨架為主的吸收被發現在約376奈米及396奈米,並在薄膜的例子中,以蒽骨架為主的吸收被發現在約381奈米及403奈米。CzPA之甲苯溶液的發射光譜(激發波長:370奈米)顯示在圖13中。CzPA之薄膜的發射光譜(激發波長:390奈米)顯示在圖14中。在圖13及14中,水平軸表示波長(奈米)及垂直軸表示發光強度 (以單元表示)。在甲苯溶液的例子中,最大發光波長為448奈米(激發波長:370奈米),並在薄膜的例子中,最大發光波長為451奈米(激發波長:390奈米)。發現獲得發藍光。 Figure 11 shows the absorption spectrum of a toluene solution of CzPA. Figure 12 shows the absorption spectrum of a film of CzPA. An ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation) was used for the measurement. The solution was placed in a quartz cell and the film sample was evaporated on a quartz substrate to form a sample. The absorption spectra from each of the reduced quartz absorption spectra are shown in Figures 11 and 12. In Figs. 11 and 12, the horizontal axis represents the wavelength (nano) and the vertical axis represents the absorption intensity (in units). In the case of the toluene solution, the absorption mainly based on the ruthenium skeleton was found to be about 376 nm and 396 nm, and in the case of the film, the absorption mainly based on the ruthenium skeleton was found at about 381 nm and 403 Nai. Meter. The emission spectrum (excitation wavelength: 370 nm) of the toluene solution of CzPA is shown in FIG. The emission spectrum (excitation wavelength: 390 nm) of the film of CzPA is shown in Fig. 14. In Figs. 13 and 14, the horizontal axis represents the wavelength (nano) and the vertical axis represents the luminous intensity. (in units). In the example of the toluene solution, the maximum emission wavelength is 448 nm (excitation wavelength: 370 nm), and in the example of the film, the maximum emission wavelength is 451 nm (excitation wavelength: 390 nm). It was found that blue light was obtained.
另外,具有薄膜態的CzPA之HOMO值為-5.64eV,其係以光電子分光計(AC-2,由Riken Keiki Co.,Ltd.所製造)在空氣中所測量。而且,吸收限係使用在圖12中的CzPA之薄膜的吸收光譜上的數據從Tauc標繪圖所獲得。當吸收限(edge)被評估為光學能隙時,該能隙為2.95eV。因此,HOMO值為-2.69eV。 Further, the HOMO value of CzPA having a film state was -5.64 eV, which was measured in the air by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.). Moreover, the absorption limit was obtained from the Tauc plot using data on the absorption spectrum of the film of CzPA in Fig. 12. When the absorption edge is evaluated as an optical energy gap, the energy gap is 2.95 eV. Therefore, the HOMO value is -2.69 eV.
而且,CzPA之氧化-還原反應特性係以循環伏安法(CV)測量法所測量。再者,電化學分析儀(ALS型600A,由BAS Inc.所製造)用於測量。 Moreover, the oxidation-reduction reaction characteristics of CzPA are measured by cyclic voltammetry (CV) measurement. Further, an electrochemical analyzer (ALS type 600A, manufactured by BAS Inc.) was used for the measurement.
脫水二甲基甲醯胺(DMF,由Aldrich所製造,99.8%,目錄編號:22705-6)被用作在CV測量法中所使用的溶液之溶劑。過氯酸四-正丁基銨(n-Bu4NClO4,由Tokyo Chemical Industry Co.,Ltd.所製造,目錄編號:T0836)為支持電解質,將其溶解在溶劑中,使得過氯酸四-正丁基銨的濃度為100毫莫耳/公升。而且,將欲測量之物體溶解,使得其濃度被設定為1毫莫耳/公升。再者,鉑電極(PTE鉑電極,由BAS Inc.所製造)被用作工作電極。鉑電極(VC-3 Pt輔助電極(5公分),由BAS Inc.所製造)被用作輔助電極。Ag/Ag+電極(RE5非水性溶劑參考電極,由BAS Inc.所製造)被用作參考電極。該 測量係在室溫下進行。應注意CV測量法的掃描速度被設定為0.1伏特/秒,而每一氧化端及還原端進行100次循環掃描。 Dehydrated dimethylformamide (DMF, manufactured by Aldrich, 99.8%, catalog number: 22705-6) was used as the solvent for the solution used in the CV measurement. Tetra-n-butylammonium perchlorate (n-Bu 4 NClO 4 , manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0836) is a supporting electrolyte, which is dissolved in a solvent to make perchloric acid The concentration of n-butylammonium is 100 millimoles per liter. Moreover, the object to be measured was dissolved so that its concentration was set to 1 millimol/liter. Further, a platinum electrode (PTE platinum electrode, manufactured by BAS Inc.) was used as the working electrode. A platinum electrode (VC-3 Pt auxiliary electrode (5 cm), manufactured by BAS Inc.) was used as the auxiliary electrode. An Ag/Ag + electrode (RE5 non-aqueous solvent reference electrode, manufactured by BAS Inc.) was used as a reference electrode. This measurement was carried out at room temperature. It should be noted that the scanning speed of the CV measurement method was set to 0.1 volt/sec, and 100 cycles of scanning were performed for each of the oxidation end and the reduction end.
圖56顯示在CzPA之還原端的CV測量法結果及圖57顯示在CzPA之氧化端的CV測量法結果。在圖56及57中,水平軸表示關於參考電極的工作電極之電位(伏特),而垂直軸表示在工作電極與輔助電極之間的電流流動值(微安培)。 Figure 56 shows the results of CV measurement at the reducing end of CzPA and Figure 57 shows the results of CV measurement at the oxidized end of CzPA. In Figs. 56 and 57, the horizontal axis represents the potential (volts) of the working electrode with respect to the reference electrode, and the vertical axis represents the current flow value (microamperes) between the working electrode and the auxiliary electrode.
在CzPA的例子中,來自圖56及57的可逆峰顯示在氧化端及還原端。另外,甚至在重複100次氧化至還原或還原至氧化循環時,峰強度不易改變。從上述發現本發明的蒽衍生物對重複的氧化-還原反應非常穩定。 In the CzPA example, the reversible peaks from Figures 56 and 57 are shown at the oxidized and reduced ends. In addition, the peak intensity is not easily changed even when the oxidation is repeated 100 times to reduction or reduction to the oxidation cycle. From the above, it has been found that the anthracene derivative of the present invention is very stable to repeated oxidation-reduction reactions.
以結構式(12)代表的9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽(縮寫:PPCzPA)之合成法被敘述於此具體實施例中。 The synthesis method of 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]anthracene (abbreviation: PPCzPA) represented by the structural formula (12) is described in this embodiment. In the example.
將9-(聯苯-4-基)蒽的合成流程顯示在(C-1)中。 The synthetic scheme of 9-(biphenyl-4-yl)anthracene is shown in (C-1).
將5.1公克(20毫莫耳)9-溴蒽、4.0公克(20毫莫耳)4-聯苯基硼酸及246毫克(0.80毫莫耳)三(鄰-甲苯基)膦放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將20毫升乙二醇二甲醚(DME)加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入45毫克(0.20毫莫耳)乙酸鈀(II)及10毫升(2.0莫耳/公升) 碳酸鉀溶液。將該反應混合物在80℃及在氮氣流下攪拌3小時。接著將反應混合物冷卻至室溫,並將沉澱之固體以抽氣過濾收集。將所收集的固體溶解在甲苯中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁而進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以乙醇再結晶,藉此獲得具有81%產率之5.4公克白色粉狀固體,其為標的物。 Put 5.1 g (20 mmol) of 9-bromoindole, 4.0 g (20 mmol) of 4-biphenylboronic acid and 246 mg (0.80 mmol) of tris(o-tolyl)phosphine into 100 ml of three In a neck flask, and carry out nitrogen substitution in the system. 20 ml of ethylene glycol dimethyl ether (DME) was added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then add 45 mg (0.20 mmol) of palladium (II) acetate and 10 ml (2.0 m / liter) Potassium carbonate solution. The reaction mixture was stirred at 80 ° C for 3 hours under a stream of nitrogen. The reaction mixture was then cooled to room temperature, and the precipitated solid was collected by suction filtration. The collected solid was dissolved in toluene, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth, and then alumina. The filtrate was condensed to give a solid, and the solid was recrystallized from ethanol, whereby 5.4 g of a white powdery solid having a yield of 81% was obtained as the subject matter.
將9-(聯苯-4-基)-10-溴蒽的合成流程顯示在(C-2)中。 The synthetic scheme of 9-(biphenyl-4-yl)-10-bromoindole is shown in (C-2).
將5.3公克(16毫莫耳)9-(聯苯-4-基)蒽及90毫升四氯化碳放入200毫升三頸燒瓶中及攪拌。將其中2.8公克(18毫莫耳)溴溶解在10毫升四氯化碳中的溶液經由滴液漏斗滴入上述溶液中。然後將溶液在室溫下攪拌1小時,並將硫代硫酸鈉水溶液加入反應溶液中,以完成反應。將反應混合物的水層以氯仿萃取,並將萃取之溶液與有機層一起以碳酸氫鈉飽和溶液及飽和食鹽水以該次序清洗。將有機層以硫酸鎂乾燥及將混合物自然過濾,以移除 硫酸鎂。接著將過濾物冷凝,獲得固體。將所獲得的固體以乙醇再結晶,藉此獲得具有82%產率之5.4公克黃色粉狀固體,其為標的物。 5.3 g (16 mmol) of 9-(biphenyl-4-yl)indole and 90 ml of carbon tetrachloride were placed in a 200 ml three-necked flask and stirred. A solution in which 2.8 g (18 mmol) of bromine was dissolved in 10 ml of carbon tetrachloride was dropped into the above solution through a dropping funnel. The solution was then stirred at room temperature for 1 hour, and an aqueous sodium thiosulfate solution was added to the reaction solution to complete the reaction. The aqueous layer of the reaction mixture was extracted with chloroform, and the extracted solution was washed with the organic layer in saturated sodium hydrogen carbonate and saturated brine. The organic layer was dried over magnesium sulfate and the mixture was filtered naturally to remove Magnesium sulfate. The filtrate was then condensed to give a solid. The solid obtained was recrystallized from ethanol, whereby 5.4 g of a yellow powdery solid having a yield of 82% was obtained, which was the subject matter.
將PPCzPA的合成流程顯示在(C-3)中。 The synthetic scheme of PPCzPA is shown in (C-3).
將3.0公克(7.3毫莫耳)9-(聯苯-4-基)-10-溴蒽及2.1公克(7.3毫莫耳)4-(咔唑-9-基)苯基硼酸放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將25毫升乙二醇二甲醚(DME)及10毫升(2.0莫耳/公升)碳酸鉀溶液加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入85毫克(0.017毫莫耳)肆(三苯膦)鈀(0)。將該反應混合物在80℃及在氮氣流下攪拌12小時。接著將反應混合物冷卻至室溫,並將沉澱之固體以抽 氣過濾收集。將所收集的固體溶解在甲苯中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以氯仿與己烷之混合溶劑再結晶,藉此獲得具有72%產率之2.9公克淺黃色粉狀固體,其為標的物。藉由核磁共振測量(NMR)確認該化合物為9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽(縮寫:PPCzPA)。 3.0 g (7.3 mmol) of 9-(biphenyl-4-yl)-10-bromoindole and 2.1 g (7.3 mmol) of 4-(carbazol-9-yl)phenylboronic acid were placed in 100 ml. In a three-necked flask, nitrogen substitution in the system was carried out. 25 ml of ethylene glycol dimethyl ether (DME) and 10 ml (2.0 mol/liter) of potassium carbonate solution were added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then 85 mg (0.017 mmol) of ruthenium (triphenylphosphine) palladium (0) was added. The reaction mixture was stirred at 80 ° C for 12 hours under a stream of nitrogen. The reaction mixture is then cooled to room temperature and the precipitated solid is pumped Gas filtration collection. The collected solid was dissolved in toluene, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth, and then alumina. The filtrate was condensed to obtain a solid, and the solid was recrystallized from a mixed solvent of chloroform and hexane, whereby 2.9 g of a pale yellow powdery solid having a yield of 72% was obtained as a target. The compound was confirmed to be 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)phenyl]anthracene (abbreviation: PPCzPA) by nuclear magnetic resonance measurement (NMR).
PPCzPA的1H NMR數據顯示於下。1H NMR(300MHz,CDCl3);δ=7.33-7.61(m,13H),7.68-7.88(m,14H),8.21(d,J=7.8Hz,2H)。1H NMR圖顯示於圖15A及15B中。應注意在圖15A中的6.5ppm至8.5ppm之範圍擴大顯示於圖15B中。 The 1 H NMR data of PPCzPA is shown below. 1 H NMR (300 MHz, CDCl 3 ); δ = 7.33 - 7.61 (m, 13H), 7.68 - 7.88 (m, 14H), 8.21. (d, J = 7.8 Hz, 2H). The 1 H NMR chart is shown in Figures 15A and 15B. It should be noted that the range expansion of 6.5 ppm to 8.5 ppm in Fig. 15A is shown in Fig. 15B.
當以上述合成方法所獲得的2.18公克PPCzPA在氬氣流動為3.0毫升/分鐘,壓力為7.0帕斯卡及加熱溫度為290℃的該等條件下昇華12小時而純化時,獲得具有74%產率之1.61公克PPCzPA之淺黃色針狀晶體。 When 2.18 g of PPCzPA obtained by the above synthesis method was purified by sublimation for 12 hours under the conditions of an argon gas flow of 3.0 ml/min, a pressure of 7.0 Pascal, and a heating temperature of 290 ° C, a yield of 74% was obtained. Light yellow needle-like crystals of 1.61 g of PPCzPA.
PPCzPA的熱重分析-微差熱分析(TG-DTA)係使用熱重分析儀/微差熱分析儀(TG/DTA 320,Seiko Instruments Inc.之產品)進行。結果,基於重力與溫度之間的關係(熱重分析測量),在正常壓力下的溫度為390℃,其為重力為95%或更低的測量開始點之重力下的溫度。發現PPCzPA具有利的耐熱性。 Thermogravimetric Analysis - Differential Thermal Analysis (TG-DTA) of PPCzPA was carried out using a thermogravimetric analyzer/differential thermal analyzer (TG/DTA 320, product of Seiko Instruments Inc.). As a result, based on the relationship between gravity and temperature (thermogravimetric analysis), the temperature under normal pressure was 390 ° C, which is the temperature under the gravity of the measurement starting point of gravity of 95% or less. PPCzPA was found to have beneficial heat resistance.
圖16顯示PPCzPA之甲苯溶液的吸收光譜。圖17顯示PPCzPA之薄膜的吸收光譜。該測量係使用UV-可見光 分光光度計(V-550,由JASCO Corporation所製造)進行。將溶液放入石英槽中及將薄膜在石英基板上蒸發,形成樣品。來自每一減掉石英吸收光譜的其吸收光譜顯示在圖16及17中。在圖16及17中,水平軸表示波長(奈米)及垂直軸表示吸收強度(以單元表示)。在甲苯溶液的例子中,以蒽骨架為主的吸收被發現在約376奈米及398奈米,並在薄膜的例子中,以蒽骨架為主的吸收被發現在約382奈米及404奈米。PPCzPA之甲苯溶液的發光光譜(激發波長:370奈米)顯示在圖18中,而PPCzPA之薄膜的發光光譜(激發波長:380奈米)顯示在圖19中。在圖18及19中,水平軸表示波長(奈米)及垂直軸表示發光強度(以單元表示)。在甲苯溶液的例子中,最大發光波長為429奈米(激發波長:370奈米),並在薄膜的例子中,其為450奈米(激發波長:380奈米)。 Figure 16 shows the absorption spectrum of a toluene solution of PPCzPA. Figure 17 shows the absorption spectrum of a film of PPCzPA. The measurement uses UV-visible light A spectrophotometer (V-550, manufactured by JASCO Corporation) was used. The solution was placed in a quartz bath and the film was evaporated on a quartz substrate to form a sample. The absorption spectra from each of the reduced quartz absorption spectra are shown in Figures 16 and 17. In Figs. 16 and 17, the horizontal axis represents the wavelength (nano) and the vertical axis represents the absorption intensity (in units). In the case of the toluene solution, the absorption mainly based on the ruthenium skeleton was found to be about 376 nm and 398 nm, and in the case of the film, the absorption mainly based on the ruthenium skeleton was found at about 382 nm and 404 Nai. Meter. The luminescence spectrum (excitation wavelength: 370 nm) of the toluene solution of PPCzPA is shown in Fig. 18, and the luminescence spectrum (excitation wavelength: 380 nm) of the film of PPCzPA is shown in Fig. 19. In Figs. 18 and 19, the horizontal axis represents the wavelength (nano) and the vertical axis represents the luminous intensity (in units of cells). In the example of the toluene solution, the maximum emission wavelength was 429 nm (excitation wavelength: 370 nm), and in the example of the film, it was 450 nm (excitation wavelength: 380 nm).
另外,具有薄膜態的PPCzPA之HOMO值為-5.59eV,其係以光電子分光計(AC-2,由Riken Keiki Co.,Ltd.所製造)在空氣中所測量。而且,吸收限係使用在圖17中的PPCzPA之薄膜的吸收光譜上的數據從Tauc標繪圖所獲得。當吸收限被評估為光學能隙時,該能隙為2.92eV。因此,HOMO值為-2.67eV。 Further, the HOMO value of PPCzPA having a film state was -5.59 eV, which was measured in the air by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.). Moreover, the absorption limit was obtained from the Tauc plot using data on the absorption spectrum of the film of PPCzPA in Fig. 17. When the absorption limit is evaluated as an optical energy gap, the energy gap is 2.92 eV. Therefore, the HOMO value is -2.67 eV.
而且,PPCzPA之氧化-還原反應特性係以循環伏安法(CV)測量法所測量。再者,電化學分析儀(ALS型600A,由BAS Inc.所製造)用於測量。 Moreover, the oxidation-reduction reaction characteristics of PPCzPA were measured by cyclic voltammetry (CV) measurement. Further, an electrochemical analyzer (ALS type 600A, manufactured by BAS Inc.) was used for the measurement.
脫水二甲基甲醯胺(DMF,由Aldrich所製造,99.8 %,目錄編號:22705-6)被用作在CV測量法中所使用的溶液之溶劑。過氯酸四-正丁基銨(n-Bu4NClO4,由Tokyo Chemical Industry Co.,Ltd.所製造,目錄編號:T0836)為支持電解質,將其溶解在溶劑中,使得過氯酸四-正丁基銨的濃度為100毫莫耳/公升。而且,將欲測量之物體溶解,使得其濃度被設定為1毫莫耳/公升。再者,鉑電極(PTE鉑電極,由BAS Inc.所製造)被用作工作電極。鉑電極(VC-3 Pt輔助電極(5公分),由BAS Inc.所製造)被用作輔助電極。Ag/Ag+電極(RE5非水性溶劑參考電極,由BAS Inc.所製造)被用作參考電極。應注意該測量係在室溫下進行。 Dehydrated dimethylformamide (DMF, manufactured by Aldrich, 99.8%, catalog number: 22705-6) was used as the solvent for the solution used in the CV measurement. Tetra-n-butylammonium perchlorate (n-Bu 4 NClO 4 , manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0836) is a supporting electrolyte, which is dissolved in a solvent to make perchloric acid The concentration of n-butylammonium is 100 millimoles per liter. Moreover, the object to be measured was dissolved so that its concentration was set to 1 millimol/liter. Further, a platinum electrode (PTE platinum electrode, manufactured by BAS Inc.) was used as the working electrode. A platinum electrode (VC-3 Pt auxiliary electrode (5 cm), manufactured by BAS Inc.) was used as the auxiliary electrode. An Ag/Ag + electrode (RE5 non-aqueous solvent reference electrode, manufactured by BAS Inc.) was used as a reference electrode. It should be noted that this measurement is carried out at room temperature.
PPCzPA之還原反應特性被測量如下。在電位從-0.47伏特改變至-2.50伏特之後,關於參考電極的工作電極之電位從-2.50伏特改變至-0.47伏特之掃描被設定為一次循環,並測量100次循環。再者,PPCzPA之氧化反應特性被測量如下。在電位從-0.33伏特改變至1.30伏特之後,關於參考電極的工作電極之電位從1.30伏特改變至-0.33伏特之掃描被設定為一次循環,並測量100次循環。再者,CV測量法的掃描速度被設定為0.1伏特/秒。 The reduction reaction characteristics of PPCzPA were measured as follows. After the potential was changed from -0.47 volts to -2.50 volts, the scan of the potential of the working electrode with respect to the reference electrode was changed from -2.50 volts to -0.47 volts, and was set to one cycle, and 100 cycles were measured. Further, the oxidation reaction characteristics of PPCzPA were measured as follows. After the potential was changed from -0.33 volts to 1.30 volts, the scan with respect to the potential of the working electrode of the reference electrode changed from 1.30 volts to -0.33 volts was set to one cycle, and 100 cycles were measured. Furthermore, the scanning speed of the CV measurement method was set to 0.1 volt/sec.
圖58顯示在PPCzPA之還原端的CV測量法結果及圖59顯示在PPCzPA之氧化端的CV測量法結果。在圖58及59中,水平軸顯示關於參考電極的工作電極之電位(伏特),而垂直軸顯示在工作電極與輔助電極之間的電流流動值(微安培)。 Figure 58 shows the results of CV measurement at the reducing end of PPCzPA and Figure 59 shows the results of CV measurement at the oxidized end of PPCzPA. In Figs. 58 and 59, the horizontal axis shows the potential (volts) of the working electrode with respect to the reference electrode, and the vertical axis shows the current flow value (microamperes) between the working electrode and the auxiliary electrode.
在PPCzPA的例子中,來自圖58及59的可逆峰顯示在氧化端及還原端。另外,甚至在重複100次氧化至還原或還原至氧化循環時,峰強度不易改變。從上述發現本發明的蒽衍生物對重複的氧化-還原反應非常穩定。 In the example of PPCzPA, the reversible peaks from Figures 58 and 59 are shown at the oxidized and reduced ends. In addition, the peak intensity is not easily changed even when the oxidation is repeated 100 times to reduction or reduction to the oxidation cycle. From the above, it has been found that the anthracene derivative of the present invention is very stable to repeated oxidation-reduction reactions.
以結構式(20)代表的9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽(縮寫:PTBCzPA)之合成法被敘述於此具體實施例中。 The synthesis method of 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]benzoquinone (abbreviation: PTBCzPA) represented by the structural formula (20) is described in this embodiment. In the example.
將9-(4-第三丁苯基)蒽的合成流程顯示在(D-1)中。 The synthetic scheme of 9-(4-t-butylphenyl)anthracene is shown in (D-1).
將5.1公克(20毫莫耳)9-溴蒽、3.6公克(20毫莫耳)4-第三丁苯基硼酸及244毫克(0.80毫莫耳)三(鄰-甲苯基)膦放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將20毫升乙二醇二甲醚(DME)加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入45毫克(0.20毫莫耳)乙酸鈀(II)及10毫升(2.0莫耳/公升)碳酸鉀溶液。將該反應混合物在80℃及在氮氣流下攪拌3小時。接著將反應混合物冷卻至室溫,並將沉澱之固體以抽氣過濾收集。將所收集的固體溶解在甲苯中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以乙醇再結晶,藉此獲得具有81%產率之5.0公克白色粉狀固體,其為標的物。 Put 5.1 grams (20 millimoles) of 9-bromoindole, 3.6 grams (20 millimoles) of 4-tert-butylphenylboronic acid and 244 milligrams (0.80 millimoles) of tris(o-tolyl)phosphine into 100 Dilute in a three-necked flask and carry out nitrogen substitution in the system. 20 ml of ethylene glycol dimethyl ether (DME) was added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then 45 mg (0.20 mmol) of palladium (II) acetate and 10 ml (2.0 mol/L) potassium carbonate solution were added. The reaction mixture was stirred at 80 ° C for 3 hours under a stream of nitrogen. The reaction mixture was then cooled to room temperature, and the precipitated solid was collected by suction filtration. The collected solid was dissolved in toluene, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth, and then alumina. The filtrate was condensed to give a solid, and the solid was recrystallized from ethanol, whereby 5.0 g of a white powdery solid having a yield of 81% was obtained as the subject matter.
將9-溴基-10-(4-第三丁苯基)蒽的合成流程顯示在(D-2)中。 The synthetic scheme of 9-bromo-10-(4-tert-butylphenyl)fluorene is shown in (D-2).
將5.0公克(16.0毫莫耳)9-(4-第三丁苯基)蒽及90毫升四氯化碳放入500毫升三頸燒瓶中及攪拌。將其中2.8公克(18毫莫耳)溴溶解在10毫升四氯化碳中的溶液經由滴液漏斗滴入上述溶液中。然後將溶液在室溫下攪拌1小時,並將硫代硫酸鈉水溶液加入反應溶液中,以完成反應。將反應混合物的水層以氯仿萃取,並將萃取之溶液與有機層一起以碳酸氫鈉飽和溶液及飽和食鹽水清洗。將有機層以硫酸鎂乾燥及將混合物自然過濾,以移除硫酸鎂。接著將過濾物冷凝,獲得固體。將所獲得的固體以乙醇再結晶,藉此獲得具有99%產率之6.3公克黃色粉狀固體,其為標的物。 5.0 g (16.0 mmol) of 9-(4-t-butylphenyl) hydrazine and 90 ml of carbon tetrachloride were placed in a 500 ml three-necked flask and stirred. A solution in which 2.8 g (18 mmol) of bromine was dissolved in 10 ml of carbon tetrachloride was dropped into the above solution through a dropping funnel. The solution was then stirred at room temperature for 1 hour, and an aqueous sodium thiosulfate solution was added to the reaction solution to complete the reaction. The aqueous layer of the reaction mixture was extracted with chloroform, and the extracted solution was washed with a saturated aqueous sodium hydrogen carbonate solution and brine. The organic layer was dried over magnesium sulfate and the mixture was filtered thoroughly to remove magnesium sulfate. The filtrate was then condensed to give a solid. The obtained solid was recrystallized from ethanol, whereby 6.3 g of a yellow powdery solid having a yield of 99% was obtained, which was the subject matter.
將PTBCzPA的合成流程顯示在(D-3)中。 The synthetic scheme of PTBCzPA is shown in (D-3).
將2.0公克(5.1莫耳)9-溴基-10-(4-第三丁苯基)蒽及1.5公克(5.1毫莫耳)4-(咔唑-9-基)苯基硼酸放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將25毫升乙二醇二甲醚(DME)及10毫升(2.0莫耳/公升)碳酸鉀溶液加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入85毫克(0.017毫莫耳)肆(三苯膦)鈀(0)。將該反應混合物在80℃及在氮氣流下攪拌12小時。接著將反應混合物冷卻至室溫,並將沉澱之固體以抽氣過濾收集。將所收集的固體溶解在甲苯中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以矽膠管柱層析法(己烷:甲苯=7:3)純化。將所得固體以己烷再結晶,藉此獲得具有32%產率之912毫克淺黃色粉狀晶體,其為標的物。藉由核磁共振測量(NMR)確認該化合物為9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽(縮寫: PTBCzPA)。 Put 2.0 g (5.1 mol) of 9-bromo-10-(4-tert-butylphenyl)fluorene and 1.5 g (5.1 mmol) of 4-(carbazol-9-yl)phenylboronic acid into 100 Dilute in a three-necked flask and carry out nitrogen substitution in the system. 25 ml of ethylene glycol dimethyl ether (DME) and 10 ml (2.0 mol/liter) of potassium carbonate solution were added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then 85 mg (0.017 mmol) of ruthenium (triphenylphosphine) palladium (0) was added. The reaction mixture was stirred at 80 ° C for 12 hours under a stream of nitrogen. The reaction mixture was then cooled to room temperature, and the precipitated solid was collected by suction filtration. The collected solid was dissolved in toluene, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth, and then alumina. The filtrate was condensed to give a solid, which was purified by silica gel column chromatography (hexane: toluene = 7:3). The obtained solid was recrystallized from hexane, whereby 912 mg of pale yellow powdery crystals having a yield of 32% was obtained as the subject matter. The compound was confirmed to be 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl)]benzoquinone by nuclear magnetic resonance measurement (NMR) (abbreviation: PTBCzPA).
PTBCzPA的1H NMR數據顯示於下。1H NMR(300MHz,CDCl3);δ=1.50(s,9H),7.33-7.54(m,10H),7.62-7.85(m,12H),8.21(d,J=7.8Hz,2H)。1H NMR圖顯示於圖20A及20B中。應注意在圖20A中的6.5ppm至8.5ppm之範圍擴大顯示於圖20B中。 The 1 H NMR data of PTBCzPA is shown below. 1 H NMR (300 MHz, CDCl 3 ); δ = 1.50 (s, 9H), 7.33 - 7.54 (m, 10H), 7.62 - 7.85 (m, 12H), 8.21. (d, J = 7.8 Hz, 2H). The 1 H NMR chart is shown in Figures 20A and 20B. It should be noted that the range expansion of 6.5 ppm to 8.5 ppm in Fig. 20A is shown in Fig. 20B.
當以上述合成方法所獲得的901毫克PTBCzPA在氬氣流動為20.0毫升/分鐘,壓力為200帕斯卡及加熱溫度為300℃的該等條件下昇華12小時而純化時,獲得具有93%產率之839毫克PTBCzPA之淺黃色針狀晶體。 When 901 mg of PTBCzPA obtained by the above synthesis method was purified by sublimation for 12 hours under the conditions of an argon gas flow of 20.0 ml/min, a pressure of 200 Pascal, and a heating temperature of 300 ° C, a yield of 93% was obtained. Light yellow needle-like crystals of 839 mg PTBCzPA.
PTBCzPA的熱重分析-微差熱分析(TG-DTA)係使用熱重分析儀/微差熱分析儀(TG/DTA 320,Seiko Instruments Inc.之產品)進行。結果,基於重力與溫度之間的關係(熱重分析測量),在正常壓力下的溫度為377℃,其為重力為95%或更低的測量開始點之重力下的溫度。發現PTBCzPA具有利的耐熱性。 Thermogravimetric Analysis - Differential Thermal Analysis (TG-DTA) of PTBCzPA was carried out using a thermogravimetric analyzer/differential thermal analyzer (TG/DTA 320, product of Seiko Instruments Inc.). As a result, based on the relationship between gravity and temperature (thermogravimetric analysis), the temperature under normal pressure was 377 ° C, which is the temperature under the gravity of the measurement starting point of gravity of 95% or less. PTBCzPA was found to have beneficial heat resistance.
圖21顯示PTBCzPA之甲苯溶液的吸收光譜。圖22顯示PTBCzPA之薄膜的吸收光譜。該測量係使用UV-可見光分光光度計(V-550,由JASCO Corporation所製造)進行。將溶液放入石英槽中及將薄膜在石英基板上蒸發,形成樣品。來自每一減掉石英吸收光譜的其吸收光譜顯示在圖21及22中。在圖21及22中,水平軸表示波長(奈米)及垂直軸表示吸收強度(以單元表示)。在甲苯溶液的例子中,以蒽骨架為主的吸收被發現在約376奈米 及396奈米,並在薄膜的例子中,以蒽骨架為主的吸收被發現在約380奈米及402奈米。PTBCzPA之甲苯溶液的發光光譜(激發波長:370奈米)顯示在圖23中,而PTBCzPA之薄膜的發光光譜(激發波長:380奈米)顯示在圖24中。在圖23及24中,水平軸表示波長(奈米)及垂直軸表示發光強度(以單元表示)。在甲苯溶液的例子中,最大發光波長為423奈米(激發波長:370奈米),並在薄膜的例子中,其為443奈米(激發波長:380奈米)。 Figure 21 shows the absorption spectrum of a toluene solution of PTBCzPA. Figure 22 shows the absorption spectrum of the film of PTBCzPA. This measurement was carried out using a UV-visible spectrophotometer (V-550, manufactured by JASCO Corporation). The solution was placed in a quartz bath and the film was evaporated on a quartz substrate to form a sample. The absorption spectra from each of the reduced quartz absorption spectra are shown in Figures 21 and 22. In Figs. 21 and 22, the horizontal axis represents the wavelength (nano) and the vertical axis represents the absorption intensity (in units). In the case of a toluene solution, the absorption based on the ruthenium skeleton was found at about 376 nm. And 396 nm, and in the case of the film, the absorption based on the ruthenium skeleton was found at about 380 nm and 402 nm. The luminescence spectrum (excitation wavelength: 370 nm) of the toluene solution of PTBCzPA is shown in Fig. 23, and the luminescence spectrum (excitation wavelength: 380 nm) of the film of PTBCzPA is shown in Fig. 24. In Figs. 23 and 24, the horizontal axis represents the wavelength (nano) and the vertical axis represents the luminous intensity (in units). In the example of the toluene solution, the maximum emission wavelength was 423 nm (excitation wavelength: 370 nm), and in the example of the film, it was 443 nm (excitation wavelength: 380 nm).
另外,具有薄膜態的PTBCzPA之HOMO值為-5.72eV,其係以光電子分光計(AC-2,由Riken Keiki Co.,Ltd.所製造)在空氣中所測量。而且,吸收限係使用在圖22中的PTBCzPA之薄膜的吸收光譜上的數據從Tauc標繪圖所獲得。當吸收限被評估為光學能隙時,該能隙為2.95eV。因此,HOMO值為-2.77eV。 Further, the HOMO value of the PTBCzPA having a film state was -5.72 eV, which was measured in the air by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.). Moreover, the absorption limit was obtained from the Tauc plot using data on the absorption spectrum of the film of PTBCzPA in Fig. 22. When the absorption limit is evaluated as an optical energy gap, the energy gap is 2.95 eV. Therefore, the HOMO value is -2.77 eV.
而且,PTBCzPA之氧化-還原反應特性係以循環伏安法(CV)測量法所測量。再者,電化學分析儀(ALS型600A,由BAS Inc.所製造)用於測量。 Moreover, the oxidation-reduction reaction characteristics of PTBCzPA were measured by cyclic voltammetry (CV) measurement. Further, an electrochemical analyzer (ALS type 600A, manufactured by BAS Inc.) was used for the measurement.
脫水二甲基甲醯胺(DMF,由Aldrich所製造,99.8%,目錄編號:22705-6)被用作在CV測量法中所使用的溶液之溶劑。過氯酸四-正丁基銨(n-Bu4NClO4,由Tokyo Chemical Industry Co.,Ltd.所製造,目錄編號:T0836)為支持電解質,將其溶解在溶劑中,使得過氯酸四-正丁基銨的濃度為100毫莫耳/公升。而且,將欲測量 之物體溶解,使得其濃度被設定為1毫莫耳/公升。再者,鉑電極(PTE鉑電極,由BAS Inc.所製造)被用作工作電極。鉑電極(VC-3 Pt輔助電極(5公分),由BAS Inc.所製造)被用作輔助電極。Ag/Ag+電極(RE5非水性溶劑參考電極,由BAS Inc.所製造)被用作參考電極。應注意該測量係在室溫下進行。 Dehydrated dimethylformamide (DMF, manufactured by Aldrich, 99.8%, catalog number: 22705-6) was used as the solvent for the solution used in the CV measurement. Tetra-n-butylammonium perchlorate (n-Bu 4 NClO 4 , manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0836) is a supporting electrolyte, which is dissolved in a solvent to make perchloric acid The concentration of n-butylammonium is 100 millimoles per liter. Moreover, the object to be measured was dissolved so that its concentration was set to 1 millimol/liter. Further, a platinum electrode (PTE platinum electrode, manufactured by BAS Inc.) was used as the working electrode. A platinum electrode (VC-3 Pt auxiliary electrode (5 cm), manufactured by BAS Inc.) was used as the auxiliary electrode. An Ag/Ag + electrode (RE5 non-aqueous solvent reference electrode, manufactured by BAS Inc.) was used as a reference electrode. It should be noted that this measurement is carried out at room temperature.
PTBCzPA之還原反應特性被測量如下。在電位從-0.25伏特改變至-2.40伏特之後,關於參考電極的工作電極之電位從-2.40伏特改變至-0.25伏特之掃描被設定為一次循環,並測量100次循環。再者,PTBCzPA之氧化反應特性被測量如下。在電位從-0.33伏特改變至1.30伏特之後,關於參考電極的工作電極之電位從1.30伏特改變至-0.33伏特之掃描被設定為一次循環,並測量100次循環。再者,CV測量法的掃描速度被設定為0.1伏特/秒。 The reduction reaction characteristics of PTBCzPA were measured as follows. After the potential was changed from -0.25 volts to -2.40 volts, the scan of the potential of the working electrode with respect to the reference electrode was changed from -2.40 volts to -0.25 volts, and was set to one cycle, and 100 cycles were measured. Further, the oxidation reaction characteristics of PTBCzPA were measured as follows. After the potential was changed from -0.33 volts to 1.30 volts, the scan with respect to the potential of the working electrode of the reference electrode changed from 1.30 volts to -0.33 volts was set to one cycle, and 100 cycles were measured. Furthermore, the scanning speed of the CV measurement method was set to 0.1 volt/sec.
圖60顯示在PTBCzPA之還原端的CV測量法結果及圖61顯示在PTBCzPA之氧化端的CV測量法結果。在圖60及61中,水平軸顯示關於參考電極的工作電極之電位(伏特),而垂直軸顯示在工作電極與輔助電極之間的電流流動值(微安培)。 Figure 60 shows the results of CV measurement at the reducing end of PTBCzPA and Figure 61 shows the results of CV measurement at the oxidized end of PTBCzPA. In Figs. 60 and 61, the horizontal axis shows the potential (volts) of the working electrode with respect to the reference electrode, and the vertical axis shows the current flow value (microamperes) between the working electrode and the auxiliary electrode.
在PTBCzPA的例子中,來自圖60及61的可逆峰顯示在氧化端及還原端。另外,甚至在重複100次氧化至還原或還原至氧化循環時,峰強度不易改變。從上述發現本發明的蒽衍生物對重複的氧化-還原反應非常穩定。 In the example of PTBCzPA, the reversible peaks from Figures 60 and 61 are shown at the oxidized and reduced ends. In addition, the peak intensity is not easily changed even when the oxidation is repeated 100 times to reduction or reduction to the oxidation cycle. From the above, it has been found that the anthracene derivative of the present invention is very stable to repeated oxidation-reduction reactions.
以結構式(42)代表的9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽(縮寫:CF3CzPA)之合成法被敘述於此具體實施例中。 The synthesis of 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethylphenyl)anthracene (abbreviation: CF3CzPA) represented by the formula (42) is described herein. In a specific embodiment.
將4-三氟甲基苯基硼酸的合成流程顯示在(E-1)中。 The synthetic scheme of 4-trifluoromethylphenylboronic acid is shown in (E-1).
將33公克(0.15莫耳)4-溴基三氟甲基苯放入500毫升三頸燒瓶中,並進行在系統中的氮取代。接著將200毫升四氫呋喃(THF)加入其中,並將混合物攪拌。將該 混合物溶液在-78℃下攪拌,並將100毫升(0.16莫耳)正丁基鋰(1.6莫耳/公升)經由滴液漏斗滴入溶液中。然後將所獲得的溶液在相同的溫度下攪拌1小時,並加入22.3毫升(0.20莫耳)硼酸三甲酯,攪拌約12小時,同時允許反應溫度逐漸增加至室溫。接著將100毫升稀釋的氫氯酸(1莫耳/公升)加入反應溶液中,並將溶液攪拌1小時。將混合物的水層使用乙酸乙酯萃取三次,將萃取之溶液與有機層一起使用飽和食鹽水清洗一次,並將有機層以硫酸鎂乾燥。將混合物自然過濾,以移除硫酸鎂,並將過濾物冷凝,獲得固體。將固體以氯仿清洗,藉此獲得具有54%產率之15公克白色固體,其為標的物。 33 g (0.15 mol) of 4-bromotrifluoromethylbenzene was placed in a 500 ml three-necked flask and subjected to nitrogen substitution in the system. Next, 200 ml of tetrahydrofuran (THF) was added thereto, and the mixture was stirred. Will The mixture solution was stirred at -78 ° C, and 100 ml (0.16 mol) of n-butyllithium (1.6 mol/liter) was dropped into the solution via a dropping funnel. The obtained solution was then stirred at the same temperature for 1 hour, and 22.3 ml (0.20 mol) of trimethyl borate was added and stirred for about 12 hours while allowing the reaction temperature to gradually increase to room temperature. Next, 100 ml of diluted hydrochloric acid (1 mol/liter) was added to the reaction solution, and the solution was stirred for 1 hour. The aqueous layer of the mixture was extracted three times with ethyl acetate. The mixture was naturally filtered to remove magnesium sulfate, and the filtrate was condensed to give a solid. The solid was washed with chloroform to give 15 g of a white solid, 54% yield, as the subject matter.
將9-(4-三氟甲基苯基)蒽的合成流程顯示在(E-2)中。 The synthetic scheme of 9-(4-trifluoromethylphenyl)fluorene is shown in (E-2).
將5.1公克(20毫莫耳)9-溴蒽、3.8公克(20毫莫耳)4-三氟甲基苯基硼酸及244毫克(0.80毫莫耳)三(鄰-甲苯基)膦放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將20毫升乙二醇二甲醚(DME)加入該 混合物中,並將混合物在減壓下攪拌及脫氣。然後加入45毫克(0.20毫莫耳)乙酸鈀(II)及10毫升(2.0莫耳/公升)碳酸鉀溶液。將該反應混合物在80℃及在氮氣流下攪拌3小時。接著將反應混合物冷卻至室溫,並將沉澱之固體以抽氣過濾收集。將所收集的固體溶解在甲苯中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以乙醇再結晶,藉此獲得具有88%產率之5.7公克白色粉狀固體,其為標的物。 Put 5.1 grams (20 millimoles) of 9-bromoindole, 3.8 grams (20 millimoles) of 4-trifluoromethylphenylboronic acid and 244 mg (0.80 millimoles) of tris(o-tolyl)phosphine A 100 ml three-necked flask was placed and subjected to nitrogen substitution in the system. Add 20 ml of ethylene glycol dimethyl ether (DME) to the The mixture was stirred and degassed under reduced pressure. Then 45 mg (0.20 mmol) of palladium (II) acetate and 10 ml (2.0 mol/L) potassium carbonate solution were added. The reaction mixture was stirred at 80 ° C for 3 hours under a stream of nitrogen. The reaction mixture was then cooled to room temperature, and the precipitated solid was collected by suction filtration. The collected solid was dissolved in toluene, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth, and then alumina. The filtrate was condensed to give a solid, and the solid was recrystallized from ethanol, whereby 5.7 g of a white powdery solid having a yield of 88% was obtained as the subject matter.
將9-溴基-10-(4-三氟甲基苯基)蒽的合成流程顯示在(E-3)中。 The synthetic scheme of 9-bromo-10-(4-trifluoromethylphenyl)fluorene is shown in (E-3).
將5.7公克(18毫莫耳)9-(4-三氟甲基苯基)蒽及90毫升四氯化碳放入500毫升三頸燒瓶中及攪拌。將其中3.2公克(20毫莫耳)溴溶解在10毫升四氯化碳中的溶液經由滴液漏斗滴入上述溶液中。然後將溶液在室溫下攪拌1小時,並將硫代硫酸鈉水溶液加入反應溶液中,以完成反應。將反應混合物的水層以氯仿萃取,並將萃取之 溶液與有機層一起以碳酸氫鈉飽和溶液及飽和食鹽水清洗。將有機層以硫酸鎂乾燥及將混合物自然過濾,以移除硫酸鎂。接著將過濾物冷凝,獲得固體。將所獲得的固體以乙醇再結晶,藉此獲得具有84%產率之5.9公克黃色粉狀固體,其為標的物。 5.7 g (18 mmol) of 9-(4-trifluoromethylphenyl)phosphonium and 90 ml of carbon tetrachloride were placed in a 500 ml three-necked flask and stirred. A solution in which 3.2 g (20 mmol) of bromine was dissolved in 10 ml of carbon tetrachloride was dropped into the above solution through a dropping funnel. The solution was then stirred at room temperature for 1 hour, and an aqueous sodium thiosulfate solution was added to the reaction solution to complete the reaction. The aqueous layer of the reaction mixture was extracted with chloroform and extracted. The solution was washed with a saturated solution of sodium hydrogencarbonate and saturated brine with an organic layer. The organic layer was dried over magnesium sulfate and the mixture was filtered thoroughly to remove magnesium sulfate. The filtrate was then condensed to give a solid. The solid obtained was recrystallized from ethanol, whereby 5.9 g of a yellow powdery solid having an 84% yield was obtained as the subject matter.
將CF3CzPA的合成流程顯示在(E-4)中。 The synthetic scheme of CF3CzPA is shown in (E-4).
將3.0公克(7.5毫莫耳)9-溴基-10-(4-三氟甲基苯基)蒽、2.2公克(7.5毫莫耳)4-(咔唑-9-基)苯基硼酸及200毫克(0.66毫莫耳)三(鄰-甲苯基)膦放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將25毫升甲苯及10毫升(2.0莫耳/公升)碳酸鉀溶液加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入60毫克(0.27毫莫耳)乙酸鈀(II)。將該反應混合物在80℃ 及在氮氣流下攪拌12小時。接著將反應混合物以水清洗三次。將混合物的水層使用乙酸乙酯萃取三次,並將萃取之溶液與有機層一起使用飽和食鹽水清洗,並將有機層以硫酸鎂乾燥。將混合物自然過濾,以移除硫酸鎂,並將過濾物冷凝,獲得固體,並將固體以矽膠管柱層析法(己烷:甲苯=65:35)純化。將所得固體以己烷再結晶,藉此獲得具有38%產率之1.6公克淺黃色粉狀固體,其為標的物。藉由核磁共振測量(NMR)確認該化合物為9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽(縮寫:CF3CzPA)。 3.0 g (7.5 mmol) of 9-bromo-10-(4-trifluoromethylphenyl)phosphonium, 2.2 g (7.5 mmol) of 4-(carbazol-9-yl)phenylboronic acid and 200 mg (0.66 mmol) of tris(o-tolyl)phosphine was placed in a 100 ml three-necked flask and subjected to nitrogen substitution in the system. 25 ml of toluene and 10 ml (2.0 mol/liter) of potassium carbonate solution were added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then 60 mg (0.27 mmol) of palladium(II) acetate was added. The reaction mixture was at 80 ° C And stirring under a nitrogen stream for 12 hours. The reaction mixture was then washed three times with water. The aqueous layer of the mixture was extracted three times with ethyl acetate, and the extracted solution was washed with brine and brine, and the organic layer was dried over magnesium sulfate. The mixture was naturally filtered to remove magnesium sulfate, and the filtrate was condensed to give a solid, and the solid was purified by silica gel column chromatography (hexane: toluene = 65:35). The obtained solid was recrystallized from hexane, whereby 1.6 g of a pale yellow powdery solid having a yield of 38% was obtained as the subject matter. The compound was confirmed to be 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethylphenyl)fluorene (abbreviation: CF3CzPA) by nuclear magnetic resonance measurement (NMR).
CF3CzPA的1H NMR數據顯示於下。1H NMR(300MHz,CDCl3);δ=7.33-7.54(m,8H),7.60-7.74(m,8H),7.83-7.92(m,6H),8.22(d,J=7.8Hz,2H)。1H NMR圖顯示於圖25A及25B中。應注意在圖25A中的6.5ppm至8.5ppm之範圍擴大顯示於圖25B中。 The 1 H NMR data of CF3CzPA is shown below. 1 H NMR (300MHz, CDCl 3 ); δ = 7.33-7.54 (m, 8H), 7.60-7.74 (m, 8H), 7.83-7.92 (m, 6H), 8.22 (d, J = 7.8Hz, 2H) . The 1 H NMR chart is shown in Figures 25A and 25B. It should be noted that the range expansion of 6.5 ppm to 8.5 ppm in Fig. 25A is shown in Fig. 25B.
當以上述合成方法所獲得的1.5公克CF3CzPA在氬氣流動為20.0毫升/分鐘,壓力為200帊斯卡及加熱溫度為300℃的該等條件下昇華12小時而純化時,獲得具有56%產率之848毫克CF3CzPA之淺黃色針狀晶體。 When 1.5 g of CF3CzPA obtained by the above synthesis method was purified by sublimation for 12 hours under the conditions of an argon gas flow of 20.0 ml/min, a pressure of 200 Torr and a heating temperature of 300 ° C, 56% yield was obtained. The pale yellow needle crystal of 848 mg CF3CzPA.
CF3CzPA的熱重分析-微差熱分析(TG-DTA)係使用熱重分析儀/微差熱分析儀(TG/DTA 320,Seiko Instruments Inc.之產品)進行。結果,基於重力與溫度之間的關係(熱重分析測量),在正常壓力下的溫度為328℃,其為重力為95%或更低的測量開始點之重力下的溫 度。發現其具有利的耐熱性。 Thermogravimetric Analysis - Differential Thermal Analysis (TG-DTA) of CF3CzPA was carried out using a thermogravimetric analyzer/differential thermal analyzer (TG/DTA 320, product of Seiko Instruments Inc.). As a result, based on the relationship between gravity and temperature (measured by thermogravimetric analysis), the temperature under normal pressure is 328 ° C, which is the temperature under the gravity of the measurement starting point of gravity of 95% or less. degree. It was found to have favorable heat resistance.
圖26顯示CF3CzPA之甲苯溶液的吸收光譜。圖27顯示CF3CzPA之薄膜的吸收光譜。該測量係使用UV-可見光分光光度計(V-550,由JASCO Corporation所製造)進行。將溶液放入石英槽中及將薄膜在石英基板上蒸發,形成樣品。來自每一減掉石英吸收光譜的其吸收光譜顯示在圖26及27中。在圖26及27中,水平軸表示波長(奈米)及垂直軸表示吸收強度(以單元表示)。在甲苯溶液的例子中,以蒽骨架為主的吸收被發現在約376奈米及396奈米,並在薄膜的例子中,以蒽骨架為主的吸收被發現在約380奈米及402奈米。CF3CzPA之甲苯溶液的發光光譜(激發波長:370奈米)顯示在圖28中,而CF3CzPA之薄膜的發光光譜(激發波長:380奈米)顯示在圖29中。在圖28及29中,水平軸表示波長(奈米)及垂直軸表示發光強度(以單元表示)。在甲苯溶液的例子中,最大發光波長為428奈米(激發波長:370奈米),並在薄膜的例子中,其為444奈米(激發波長:380奈米)。 Figure 26 shows the absorption spectrum of a toluene solution of CF3CzPA. Figure 27 shows the absorption spectrum of a film of CF3CzPA. This measurement was carried out using a UV-visible spectrophotometer (V-550, manufactured by JASCO Corporation). The solution was placed in a quartz bath and the film was evaporated on a quartz substrate to form a sample. The absorption spectra from each of the reduced quartz absorption spectra are shown in Figures 26 and 27. In Figs. 26 and 27, the horizontal axis represents the wavelength (nano) and the vertical axis represents the absorption intensity (in units). In the case of the toluene solution, the absorption mainly based on the ruthenium skeleton was found to be about 376 nm and 396 nm, and in the case of the film, the absorption mainly based on the ruthenium skeleton was found at about 380 nm and 402 Nai. Meter. The luminescence spectrum (excitation wavelength: 370 nm) of the toluene solution of CF3CzPA is shown in Fig. 28, and the luminescence spectrum (excitation wavelength: 380 nm) of the film of CF3CzPA is shown in Fig. 29. In Figs. 28 and 29, the horizontal axis represents the wavelength (nano) and the vertical axis represents the luminous intensity (in units). In the example of the toluene solution, the maximum emission wavelength was 428 nm (excitation wavelength: 370 nm), and in the example of the film, it was 444 nm (excitation wavelength: 380 nm).
另外,具有薄膜態的CF3CzPA之HOMO值為-6.01eV,其係以光電子分光計(AC-2,由Riken Keiki Co.,Ltd.所製造)在空氣中所測量。而且,吸收限係使用在圖27中的CF3CzPA之薄膜的吸收光譜上的數據從Tauc標繪圖所獲得。當吸收限被評估為光學能隙時,該能隙為2.95eV。因此,HOMO值為-3.06eV。 Further, the HOMO value of CF3CzPA having a film state was -6.01 eV, which was measured in the air by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.). Moreover, the absorption limit was obtained from the Tauc plot using data on the absorption spectrum of the CF3CzPA film of Fig. 27. When the absorption limit is evaluated as an optical energy gap, the energy gap is 2.95 eV. Therefore, the HOMO value is -3.06 eV.
而且,CF3CzPA之氧化-還原反應特性係以循環伏安法(CV)測量法所測量。再者,電化學分析儀(ALS型600A,由BAS Inc.所製造)用於測量。 Moreover, the oxidation-reduction reaction characteristics of CF3CzPA were measured by cyclic voltammetry (CV) measurement. Further, an electrochemical analyzer (ALS type 600A, manufactured by BAS Inc.) was used for the measurement.
脫水二甲基甲醯胺(DMF,由Aldrich所製造,99.8%,目錄編號:22705-6)被用作在CV測量法中所使用的溶液之溶劑。過氯酸四-正丁基銨(n-Bu4NClO4,由Tokyo Chemical Industry Co.,Ltd.所製造,目錄編號:T0836)為支持電解質,將其溶解在溶劑中,使得過氯酸四-正丁基銨的濃度為100毫莫耳/公升。而且,將欲測量之物體溶解,使得其濃度被設定為1毫莫耳/公升。再者,鉑電極(PTE鉑電極,由BAS Inc.所製造)被用作工作電極。鉑電極(VC-3 Pt輔助電極(5公分),由BAS Inc.所製造)被用作輔助電極。Ag/Ag+電極(RE5非水性溶劑參考電極,由BAS Inc.所製造)被用作參考電極。應注意該測量係在室溫下進行。 Dehydrated dimethylformamide (DMF, manufactured by Aldrich, 99.8%, catalog number: 22705-6) was used as the solvent for the solution used in the CV measurement. Tetra-n-butylammonium perchlorate (n-Bu 4 NClO 4 , manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0836) is a supporting electrolyte, which is dissolved in a solvent to make perchloric acid The concentration of n-butylammonium is 100 millimoles per liter. Moreover, the object to be measured was dissolved so that its concentration was set to 1 millimol/liter. Further, a platinum electrode (PTE platinum electrode, manufactured by BAS Inc.) was used as the working electrode. A platinum electrode (VC-3 Pt auxiliary electrode (5 cm), manufactured by BAS Inc.) was used as the auxiliary electrode. An Ag/Ag + electrode (RE5 non-aqueous solvent reference electrode, manufactured by BAS Inc.) was used as a reference electrode. It should be noted that this measurement is carried out at room temperature.
CF3CzPA之還原反應特性被測量如下。在電位從-0.18伏特改變至-2.23伏特之後,關於參考電極的工作電極之電位從-2.23伏特改變至-0.18伏特之掃描被設定為一次循環,並測量100次循環。再者,CF3CzPA之氧化反應特性被測量如下。在電位從-0.27伏特改變至1.30伏特之後,關於參考電極的工作電極之電位從1.30伏特改變至-0.27伏特之掃描被設定為一次循環,並測量100次循環。再者,CV測量法的掃描速度被設定為0.1伏特/秒。 The reduction reaction characteristics of CF3CzPA were measured as follows. After the potential was changed from -0.18 volts to -2.22 volts, the scan of the potential of the working electrode with respect to the reference electrode was changed from -2.32 volts to -0.18 volts, and one cycle was measured, and 100 cycles were measured. Further, the oxidation reaction characteristics of CF3CzPA were measured as follows. After the potential was changed from -0.27 volts to 1.30 volts, the scan with respect to the potential of the working electrode of the reference electrode changed from 1.30 volts to -0.27 volts was set to one cycle, and 100 cycles were measured. Furthermore, the scanning speed of the CV measurement method was set to 0.1 volt/sec.
圖62顯示在CF3CzPA之還原端的CV測量法結果及 圖63顯示在CF3CzPA之氧化端的CV測量法結果。在圖62及63中,水平軸顯示關於參考電極的工作電極之電位(伏特),而垂直軸顯示在工作電極與輔助電極之間的電流流動值(微安培)。 Figure 62 shows the results of CV measurement at the reducing end of CF3CzPA and Figure 63 shows the results of CV measurement at the oxidation end of CF3CzPA. In Figs. 62 and 63, the horizontal axis shows the potential (volts) of the working electrode with respect to the reference electrode, and the vertical axis shows the current flow value (microamperes) between the working electrode and the auxiliary electrode.
在CF3CzPA的例子中,來自圖62及63的可逆峰顯示在氧化端及還原端。另外,甚至在重複100次氧化至還原或還原至氧化循環時,峰強度不易改變。從上述發現本發明的蒽衍生物對重複的氧化-還原反應非常穩定。 In the CF3CzPA example, the reversible peaks from Figures 62 and 63 are shown at the oxidized and reduced ends. In addition, the peak intensity is not easily changed even when the oxidation is repeated 100 times to reduction or reduction to the oxidation cycle. From the above, it has been found that the anthracene derivative of the present invention is very stable to repeated oxidation-reduction reactions.
以結構式(16)代表的9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽(縮寫:β NCzPA)之合成法被敘述於此具體實施例中。 The synthesis method of 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene (abbreviation: β NCzPA) represented by the structural formula (16) is described in this specific example. in.
將9-(2-萘基)蒽的合成流程顯示在(F-1)中。 The synthetic scheme of 9-(2-naphthyl)anthracene is shown in (F-1).
將5.1公克(20毫莫耳)9-溴蒽、3.4公克(20毫莫耳)2-萘基硼酸及244毫克(0.80毫莫耳)三(鄰-甲苯基)膦放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將20毫升乙二醇二甲醚(DME)加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入45毫克(0.20毫莫耳)乙酸鈀(II)及10毫升(2.0莫耳/公升)碳酸鉀溶液。將該反應混合物在80℃及在氮氣流下攪拌3小時。接著將反應混合物冷卻至室溫,並將沉澱之固體以抽氣過濾收集。將所收集的固體溶解在甲苯中,並使溶液通過矽酸鎂、矽藻土及接著氧化鋁進行抽氣過濾。將過濾物冷凝,獲得固體,並將固體以乙醇再結晶,藉此獲得具有92%產率之5.6公克白色粉狀固體,其為標的物。 Put 5.1 g (20 mmol) of 9-bromoindole, 3.4 g (20 mmol) of 2-naphthylboronic acid and 244 mg (0.80 mmol) of tris(o-tolyl)phosphine into 100 ml three necks In the flask, and carry out nitrogen substitution in the system. 20 ml of ethylene glycol dimethyl ether (DME) was added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then 45 mg (0.20 mmol) of palladium (II) acetate and 10 ml (2.0 mol/L) potassium carbonate solution were added. The reaction mixture was stirred at 80 ° C for 3 hours under a stream of nitrogen. The reaction mixture was then cooled to room temperature, and the precipitated solid was collected by suction filtration. The collected solid was dissolved in toluene, and the solution was subjected to suction filtration through magnesium ruthenate, diatomaceous earth, and then alumina. The filtrate was condensed to give a solid, and the solid was recrystallized from ethanol, whereby 5.6 g of a white powdery solid having a yield of 92% was obtained as the subject matter.
將9-溴基-10-(2-萘基)蒽的合成流程顯示在(F-2)中。 The synthetic scheme of 9-bromo-10-(2-naphthyl)anthracene is shown in (F-2).
將5.6公克(18.0毫莫耳)9-(2-萘基)蒽及90毫升四氯化碳放入500毫升三頸燒瓶中及攪拌。將其中3.2公克(20毫莫耳)溴溶解在10毫升四氯化碳中的溶液經由滴液漏斗滴入上述溶液中。然後將溶液在室溫下攪拌1小時,並將硫代硫酸鈉水溶液加入反應溶液中,以完成反應。將反應混合物的水層以氯仿萃取,並將萃取之溶液與有機層一起以碳酸氫鈉飽和溶液及飽和食鹽水清洗。將有機層以硫酸鎂乾燥及將混合物自然過濾,以移除硫酸鎂。接著將過濾物冷凝,獲得固體。將所獲得的固體以乙醇再結晶,藉此獲得具有79%產率之5.5公克黃色粉狀固體,其為標的物。 5.6 g (18.0 mmol) of 9-(2-naphthyl)anthracene and 90 ml of carbon tetrachloride were placed in a 500 ml three-necked flask and stirred. A solution in which 3.2 g (20 mmol) of bromine was dissolved in 10 ml of carbon tetrachloride was dropped into the above solution through a dropping funnel. The solution was then stirred at room temperature for 1 hour, and an aqueous sodium thiosulfate solution was added to the reaction solution to complete the reaction. The aqueous layer of the reaction mixture was extracted with chloroform, and the extracted solution was washed with a saturated aqueous sodium hydrogen carbonate solution and brine. The organic layer was dried over magnesium sulfate and the mixture was filtered thoroughly to remove magnesium sulfate. The filtrate was then condensed to give a solid. The solid obtained was recrystallized from ethanol, whereby 5.5 g of a yellow powdery solid having a yield of 79% was obtained as the subject matter.
將β NCzPA的合成流程顯示在(F-3)中。 The synthetic scheme of β NCzPA is shown in (F-3).
將3.0公克(7.8毫莫耳)9-溴基-10-(2-萘基)蒽及2.3公克(7.8毫莫耳)4-(咔唑-9-基)苯基硼酸放入100毫升三頸燒瓶中,並進行在系統中的氮取代。將25毫升乙二醇二甲醚(DME)及10毫升(2.0莫耳/公升)碳酸鉀溶液加入該混合物中,並將混合物在減壓下攪拌及脫氣。然後加入90毫克(0.017毫莫耳)肆(三苯膦)鈀(0)。將該反應混合物在80℃及在氮氣流下攪拌12小時。接著將反應混合物以水清洗。將混合物的水層使用乙酸乙酯萃取,並將萃取之溶液與有機層一起使用飽和食鹽水清洗,並將有機層以硫酸鎂乾燥。將混合物自然過濾,以移除硫酸鎂。將過濾物冷凝,獲得固體,並將固體以矽膠管柱層析法(己烷:甲苯=7:3)純化。將所得固體以己烷再結晶,藉此獲得具有57%產率之2.4公克淺黃色固體,其為標的物。藉由核磁共振測量(NMR)確認該化合物為9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽(縮寫:β NCzPA)。 3.0 g (7.8 mmol) of 9-bromo-10-(2-naphthyl)anthracene and 2.3 g (7.8 mmol) of 4-(carbazol-9-yl)phenylboronic acid were placed in 100 ml of three In a neck flask, and carry out nitrogen substitution in the system. 25 ml of ethylene glycol dimethyl ether (DME) and 10 ml (2.0 mol/liter) of potassium carbonate solution were added to the mixture, and the mixture was stirred and degassed under reduced pressure. Then 90 mg (0.017 mmol) of ruthenium (triphenylphosphine) palladium (0) was added. The reaction mixture was stirred at 80 ° C for 12 hours under a stream of nitrogen. The reaction mixture was then washed with water. The aqueous layer of the mixture was extracted with ethyl acetate, and the extracted solution was washed with brine and brine and dried over magnesium sulfate. The mixture was naturally filtered to remove magnesium sulfate. The filtrate was condensed to give a solid, which was purified by silica gel column chromatography (hexane: toluene = 7:3). The obtained solid was recrystallized from hexane, whereby 2.4 g of a pale yellow solid with a yield of 57% was obtained as the subject matter. The compound was confirmed to be 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl)anthracene (abbreviation: β NCzPA) by nuclear magnetic resonance measurement (NMR).
β NCzPA的1H NMR數據顯示於下。1H NMR(300MHz,CDCl3);δ=7.33-7.56(m,9H),7.59-7.78(m,9H),7.83-7.89(m,4H),7.92-7.95(m,1H),8.01-8.06(m,2H),8.10(d,J=8.7Hz,1H),8.22(d,J=7.2Hz,2H)。1H NMR圖顯示於圖30A及30B中。應注意在圖30A中的6.5ppm至8.5ppm之範圍擴大顯示於圖30B中。 The 1 H NMR data of β NCzPA is shown below. 1 H NMR (300 MHz, CDCl 3 ); δ=7.33-7.56 (m, 9H), 7.59-7.78 (m, 9H), 7.83-7.89 (m, 4H), 7.92-7.95 (m, 1H), 8.01 8.06 (m, 2H), 8.10 (d, J = 8.7 Hz, 1H), 8.22 (d, J = 7.2 Hz, 2H). The 1 H NMR chart is shown in Figures 30A and 30B. It should be noted that the range expansion of 6.5 ppm to 8.5 ppm in Fig. 30A is shown in Fig. 30B.
當以上述合成方法所獲得的1.79公克β NCzPA在氬氣流動為3.0毫升/分鐘,壓力為8.0帕斯卡及加熱溫度為290℃的該等條件下昇華12小時而純化時,獲得具有89%產率之1.59公克β NCzPA之淺黃色針狀晶體。 When 1.79 g of β NCzPA obtained by the above synthesis method was purified by sublimation for 12 hours under the conditions of an argon gas flow of 3.0 ml/min, a pressure of 8.0 Pascal and a heating temperature of 290 ° C, an 89% yield was obtained. 1.59 grams of light yellow needle crystal of β NCzPA.
β NCzPA的熱重分析-微差熱分析(TG/DTA)係使用熱重分析儀/微差熱分析儀(TG/DTA 320,Seiko Instruments Inc.之產品)進行。結果,基於重力與溫度之間的關係(熱重分析測量),在正常壓力下的溫度為368℃,其為重力為95%或更低的測量開始點之重力下的溫度。發現其具有利的耐熱性。 Thermogravimetric Analysis - Differential Thermal Analysis (TG/DTA) of β NCzPA was carried out using a thermogravimetric analyzer/differential thermal analyzer (TG/DTA 320, product of Seiko Instruments Inc.). As a result, based on the relationship between gravity and temperature (thermogravimetric analysis), the temperature under normal pressure was 368 ° C, which is the temperature under the gravity of the measurement starting point of gravity of 95% or less. It was found to have favorable heat resistance.
圖31顯示β NCzPA之甲苯溶液的吸收光譜。圖32顯示β NCzPA之薄膜的吸收光譜。該測量係使用UV-可見光分光光度計(V-550,由JASCO Corporation所製造)進行。將溶液放入石英槽中及將薄膜在石英基板上蒸發,形成樣品。來自每一減掉石英吸收光譜的其吸收光譜顯示在圖31及32中。在圖31及31中,水平軸表示波長(奈米),而垂直軸表示吸收強度(以單元表示)。在甲苯溶 液的例子中,以蒽骨架為主的吸收被發現在約378奈米及398奈米,並在薄膜的例子中,以蒽骨架為主的吸收被發現在約384奈米及404奈米。β NCzPA之甲苯溶液的發光光譜(激發波長:370奈米)顯示在圖33中,而β NCzPA之薄膜的發光光譜(激發波長:381奈米)顯示在圖34中。在圖33及34中,水平軸表示波長(奈米)及垂直軸表示發光強度(以單元表示)。在甲苯溶液的例子中,最大發光波長為426奈米(激發波長:370奈米),並在薄膜的例子中,其為440奈米(激發波長:381奈米)。 Figure 31 shows the absorption spectrum of a toluene solution of β NCzPA. Figure 32 shows the absorption spectrum of a film of β NCzPA. This measurement was carried out using a UV-visible spectrophotometer (V-550, manufactured by JASCO Corporation). The solution was placed in a quartz bath and the film was evaporated on a quartz substrate to form a sample. The absorption spectra from each of the reduced quartz absorption spectra are shown in Figures 31 and 32. In Figs. 31 and 31, the horizontal axis represents the wavelength (nano), and the vertical axis represents the absorption intensity (in units). In toluene In the case of the liquid, the absorption mainly based on the ruthenium skeleton was found to be about 378 nm and 398 nm, and in the case of the film, the absorption mainly based on the ruthenium skeleton was found at about 384 nm and 404 nm. The luminescence spectrum (excitation wavelength: 370 nm) of the toluene solution of β NCzPA is shown in Fig. 33, and the luminescence spectrum (excitation wavelength: 381 nm) of the film of β NCzPA is shown in Fig. 34 . In Figs. 33 and 34, the horizontal axis represents the wavelength (nano) and the vertical axis represents the luminous intensity (in units). In the example of the toluene solution, the maximum emission wavelength was 426 nm (excitation wavelength: 370 nm), and in the example of the film, it was 440 nm (excitation wavelength: 381 nm).
另外,具有薄膜態的β NCzPA之HOMO值為-5.72eV,其係以光電子分光計(AC-2,由Riken Keiki Co.,Ltd.所製造)在空氣中所測量。而且,吸收限係使用在圖32中的β NCzPA之薄膜的吸收光譜上的數據從Tauc標繪圖所獲得。當吸收限被評估為光學能隙時,該能隙為2.92eV。因此,HOMO值為-2.80eV。 Further, the HOMO value of β NCzPA having a film state was -5.72 eV, which was measured in the air by a photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.). Moreover, the absorption limit was obtained from the Tauc plot using data on the absorption spectrum of the film of β NCzPA in Fig. 32. When the absorption limit is evaluated as an optical energy gap, the energy gap is 2.92 eV. Therefore, the HOMO value is -2.80 eV.
而且,β NCzPA之氧化-還原反應特性係以循環伏安法(CV)測量法所測量。再者,電化學分析儀(ALS型600A,由BAS Inc.所製造)用於測量。 Moreover, the oxidation-reduction reaction characteristics of β NCzPA were measured by cyclic voltammetry (CV) measurement. Further, an electrochemical analyzer (ALS type 600A, manufactured by BAS Inc.) was used for the measurement.
脫水二甲基甲醯胺(DMF,由Aldrich所製造,99.8%,目錄編號:22705-6)被用作在CV測量法中所使用的溶液之溶劑。過氯酸四-正丁基銨(n-Bu4NClO4,由Tokyo Chemical Industry Co.,Ltd.所製造,目錄編號:T0836)為支持電解質,將其溶解在溶劑中,使得過氯酸 四-正丁基銨的濃度為100毫莫耳/公升。而且,將欲測量之物體溶解,使得其濃度被設定為1毫莫耳/公升。再者,鉑電極(PTE鉑電極,由BAS Inc.所製造)被用作工作電極。鉑電極(VC-3 Pt輔助電極(5公分),由BAS Inc.所製造)被用作輔助電極。Ag/Ag+電極(RE5非水性溶劑參考電極,由BAS Inc.所製造)被用作參考電極。應注意該測量係在室溫下進行。 Dehydrated dimethylformamide (DMF, manufactured by Aldrich, 99.8%, catalog number: 22705-6) was used as the solvent for the solution used in the CV measurement. Tetra-n-butylammonium perchlorate (n-Bu 4 NClO 4 , manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0836) is a supporting electrolyte, which is dissolved in a solvent to make perchloric acid The concentration of n-butylammonium is 100 millimoles per liter. Moreover, the object to be measured was dissolved so that its concentration was set to 1 millimol/liter. Further, a platinum electrode (PTE platinum electrode, manufactured by BAS Inc.) was used as the working electrode. A platinum electrode (VC-3 Pt auxiliary electrode (5 cm), manufactured by BAS Inc.) was used as the auxiliary electrode. An Ag/Ag + electrode (RE5 non-aqueous solvent reference electrode, manufactured by BAS Inc.) was used as a reference electrode. It should be noted that this measurement is carried out at room temperature.
β NCzPA之還原反應特性被測量如下。在電位從-0.24伏特改變至-2.40伏特之後,關於參考電極的工作電極之電位從-2.40伏特改變至-0.24伏特之掃描被設定為一次循環,並測量100次循環。再者,β NCzPA之氧化反應特性被測量如下。在電位從-0.30伏特改變至1.20伏特之後,關於參考電極的工作電極之電位從1.20伏特改變至-0.30伏特之掃描被設定為一次循環,並測量100次循環。再者,CV測量法的掃描速度被設定為0.1伏特/秒。 The reduction reaction characteristics of β NCzPA were measured as follows. After the potential was changed from -0.24 volts to -2.40 volts, the scan of the potential of the working electrode with respect to the reference electrode was changed from -2.40 volts to -0.24 volts, and was set to one cycle, and 100 cycles were measured. Further, the oxidation reaction characteristics of β NCzPA were measured as follows. After the potential was changed from -0.30 volts to 1.20 volts, the scan with respect to the potential of the working electrode of the reference electrode changed from 1.20 volts to -0.30 volts was set to one cycle, and 100 cycles were measured. Furthermore, the scanning speed of the CV measurement method was set to 0.1 volt/sec.
圖64顯示在β NCzPA之還原端的CV測量法結果及圖65顯示在β NCzPA之氧化端的CV測量法結果。在圖64及65中,水平軸顯示關於參考電極的工作電極之電位(伏特),而垂直軸顯示在工作電極與輔助電極之間的電流流動值(微安培)。 Figure 64 shows the results of CV measurement at the reducing end of β NCzPA and Figure 65 shows the results of CV measurement at the oxidation end of β NCzPA. In Figs. 64 and 65, the horizontal axis shows the potential (volts) of the working electrode with respect to the reference electrode, and the vertical axis shows the current flow value (microamperes) between the working electrode and the auxiliary electrode.
在β NCzPA的例子中,來自圖64及65的可逆峰顯示在氧化端及還原端。另外,甚至在重複100次氧化至還原或還原至氧化循環時,峰強度不易改變。從上述發現本發明的蒽衍生物對重複的氧化-還原反應非常穩定。 In the example of β NCzPA, the reversible peaks from Figures 64 and 65 are shown at the oxidized end and the reduced end. In addition, the peak intensity is not easily changed even when the oxidation is repeated 100 times to reduction or reduction to the oxidation cycle. From the above, it has been found that the anthracene derivative of the present invention is very stable to repeated oxidation-reduction reactions.
本發明的發光元件以參考圖55被敘述於此具體實施例中。在此具體實施例中所使用的材料之化學式顯示於下。 The light-emitting element of the present invention is described in this specific embodiment with reference to FIG. The chemical formula of the materials used in this embodiment is shown below.
用於製造此具體實施例的發光元件之方法顯示於下。 The method for producing the light-emitting element of this embodiment is shown below.
首先,將含有氧化矽的氧化銦錫(ITSO)藉由濺鍍法沉積在玻璃基板2101上,得以形成第一個電極2102。應注意其厚度為110奈米及電極面積為2奈米x 2奈米。 First, indium tin oxide (ITSO) containing ruthenium oxide is deposited on the glass substrate 2101 by sputtering to form the first electrode 2102. It should be noted that the thickness is 110 nm and the electrode area is 2 nm x 2 nm.
接著,將於其上形成第一個電極的基板固定於真空蒸發裝置中提供的基板固定架上,以該方式使得基板表面具有面朝下的第一個電極。將電壓減低至約10-4帊斯卡,並接著將4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)及氧化鉬(VI)共同蒸發在第一個電極2102上,藉此形成含有有機化合物與無機化合物之複合材料的層2103。層2103的膜厚度為50奈米,並且介於NPB與氧化鉬(VI)之間的重量比被設定為4:1(=NPB:氧化鉬)。應注意共同蒸發法為其中蒸發係在一個處理室中同時以數個蒸發源進行的蒸發方法。 Next, the substrate on which the first electrode is formed is fixed to the substrate holder provided in the vacuum evaporation apparatus in such a manner that the surface of the substrate has the first electrode facing downward. The voltage is reduced to about 10 -4 Å, and then 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB) and molybdenum oxide (VI) are common. Evaporation is performed on the first electrode 2102, thereby forming a layer 2103 containing a composite material of an organic compound and an inorganic compound. The film thickness of the layer 2103 was 50 nm, and the weight ratio between NPB and molybdenum oxide (VI) was set to 4:1 (= NPB: molybdenum oxide). It should be noted that the co-evaporation method is an evaporation method in which an evaporation system is carried out in one processing chamber while being performed by several evaporation sources.
接著,具有厚度10萘米的電洞傳輸層2104係藉由使用耐熱的蒸發法使用4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)而形成於含有複合材料的層2103上。 Next, the hole transport layer 2104 having a thickness of 10 nm is used by using a heat-resistant evaporation method using 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB). It is formed on the layer 2103 containing the composite material.
再者,具有厚度30萘米的發光層2105係藉由共同蒸發以結構式(11)代表的9-〔4-(N-咔唑基)〕苯基-10-苯蒽(縮寫:CzPA)及N,N’-雙〔4-(9H-咔唑-9-基)苯基〕-N,N’-二苯茋-4,4’-二胺(縮寫:YGA2S)而形成於電洞傳輸層2104上。在此介於CzPA與YGA2S之間的重量比被調整為1:0.05(=CzPA:YGA2S)。 Further, the light-emitting layer 2105 having a thickness of 30 nm is a 9-[4-(N-carbazolyl)]phenyl-10-benzoquinone represented by the structural formula (11) by co-evaporation (abbreviation: CzPA) And N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylindole-4,4'-diamine (abbreviation: YGA2S) formed in a hole On the transport layer 2104. Here, the weight ratio between CzPA and YGA2S was adjusted to 1:0.05 (= CzPA: YGA2S).
接著,具有厚度10萘米的電子傳輸層2106係藉由使用耐熱的蒸發法使用參(5-喹啉)絡鋁(縮寫:Alq)而形成於發光層2105上。 Next, an electron transport layer 2106 having a thickness of 10 nm was formed on the light-emitting layer 2105 by using a heat-resistant evaporation method using quinone (5-quinoline) complex aluminum (abbreviation: Alq).
而且,具有厚度20萘米的電子注射層2107係藉由共 同蒸發參(5-喹啉)絡鋁(縮寫:Alq)及鋰而形成於電子傳輸層2106。在此介於Alq與鋰之間的重量比被調整為1:0.01(=Alq:鋰)。 Moreover, an electron injection layer 2107 having a thickness of 20 nm is used by a total of The electron transport layer 2106 is formed by evaporating ginseng (5-quinoline) complex aluminum (abbreviation: Alq) and lithium. Here, the weight ratio between Alq and lithium was adjusted to 1:0.01 (=Alq: lithium).
接著,具有厚度200萘米的第二個電極2108係藉由使用耐熱的蒸發法而形成於電子注射層2107上。因此,製造發光元件1。 Next, a second electrode 2108 having a thickness of 200 nm is formed on the electron injection layer 2107 by a heat-resistant evaporation method. Therefore, the light-emitting element 1 is manufactured.
圖35顯示發光元件1的電流密度對亮度特性,圖36顯示其電壓對亮度特性及圖37顯示其亮度對電流效率特性。再者,圖38顯示在1毫安培電流下所獲得的發射光譜。發光元件1在1064cd/平方公尺之亮度下的CIE色度座標為(x=0.17,y=0.20)及發光為藍色。在1064cd/平方公尺之亮度下的電流效率為4.8cd/安培,且同時電壓為5.8伏特及電流密度為22.2毫安培/平方公分。另外,如圖38所示,在1毫安培電流下的最大發射波長為444奈米。 Fig. 35 shows the current density versus luminance characteristics of the light-emitting element 1, Fig. 36 shows its voltage versus luminance characteristics, and Fig. 37 shows its luminance versus current efficiency characteristics. Again, Figure 38 shows the emission spectra obtained at a current of 1 milliamperes. The CIE chromaticity coordinates of the light-emitting element 1 at a luminance of 1064 cd/m 2 are (x = 0.17, y = 0.20) and the luminescence is blue. The current efficiency at a luminance of 1064 cd/m 2 was 4.8 cd/ampere, and at the same time, the voltage was 5.8 volts and the current density was 22.2 mA/cm 2 . In addition, as shown in FIG. 38, the maximum emission wavelength at a current of 1 milliamperes is 444 nm.
本發明的發光元件以參考圖55被敘述於此具體實施例中。用於製造此具體實施例的發光元件之方法顯示於下。 The light-emitting element of the present invention is described in this specific embodiment with reference to FIG. The method for producing the light-emitting element of this embodiment is shown below.
首先,將含有氧化矽的氧化銦錫(ITSO)藉由濺鍍法沉積在玻璃基板2101上,得以形成第一個電極2102。應注意其厚度為110奈米及電極面積為2奈米x 2奈米。 First, indium tin oxide (ITSO) containing ruthenium oxide is deposited on the glass substrate 2101 by sputtering to form the first electrode 2102. It should be noted that the thickness is 110 nm and the electrode area is 2 nm x 2 nm.
接著,將於其上形成第一個電極的基板固定於真空蒸 發裝置中提供的基板固定架上,以該方式使得基板表面具有面朝下的第一個電極。將電壓減低至約10-4帊斯卡,並接著將4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)及氧化鉬(VI)共同蒸發在第一個電極2102上,藉此形成含有有機化合物與無機化合物之複合材料的層2103。層2103的膜厚度為50奈米,並且介於NPB與氧化鉬(VI)之間的重量比被設定為4:1(=NPB:氧化鉬)。應注意共同蒸發法為其中蒸發係在一個處理室中同時以數個蒸發源進行的蒸發方法。 Next, the substrate on which the first electrode is formed is fixed to the substrate holder provided in the vacuum evaporation apparatus in such a manner that the surface of the substrate has the first electrode facing downward. The voltage is reduced to about 10 -4 Å, and then 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB) and molybdenum oxide (VI) are common. Evaporation is performed on the first electrode 2102, thereby forming a layer 2103 containing a composite material of an organic compound and an inorganic compound. The film thickness of the layer 2103 was 50 nm, and the weight ratio between NPB and molybdenum oxide (VI) was set to 4:1 (= NPB: molybdenum oxide). It should be noted that the co-evaporation method is an evaporation method in which an evaporation system is carried out in one processing chamber while being performed by several evaporation sources.
接著,具有厚度10萘米的電洞傳輸層2104係藉由使用耐熱的蒸發法使用4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)而形成於含有複合材料的層2103上。 Next, the hole transport layer 2104 having a thickness of 10 nm is used by using a heat-resistant evaporation method using 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB). It is formed on the layer 2103 containing the composite material.
再者,具有厚度30萘米的發光層2105係藉由共同蒸發以結構式(12)代表的9-(聯苯-4-基)-10-〔4-(咔唑-9-基)苯基〕蒽(縮寫:PPCzPA)及N,N’-雙〔4-(9H-咔唑-9-基)苯基〕-N,N’-二苯茋-4,4’-二胺(縮寫:YGA2S)而形成於電洞傳輸層2104上。在此介於PPCzPA與YGA2S之間的重量比被調整為1:0.05(=PPCzPA:YGA2S)。 Further, the light-emitting layer 2105 having a thickness of 30 nm is a 9-(biphenyl-4-yl)-10-[4-(carbazol-9-yl)benzene represented by the structural formula (12) by co-evaporation.蒽] (abbreviation: PPCzPA) and N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylindole-4,4'-diamine (abbreviation :YGA2S) is formed on the hole transport layer 2104. Here, the weight ratio between PPCzPA and YGA2S was adjusted to 1:0.05 (=PPCzPA: YGA2S).
接著,具有厚度10萘米的電子傳輸層2106係藉由使用耐熱的蒸發法使用參(5-喹啉)絡鋁(縮寫:Alq)而形成於發光層2105上。 Next, an electron transport layer 2106 having a thickness of 10 nm was formed on the light-emitting layer 2105 by using a heat-resistant evaporation method using quinone (5-quinoline) complex aluminum (abbreviation: Alq).
而且,具有厚度20萘米的電子注射層2107係藉由共 同蒸發參(5-喹啉)絡鋁(縮寫:Alq)及鋰而形成於電子傳輸層2106。在此介於Alq與鋰之間的重量比被調整為1:0.01(=Alq:鋰)。 Moreover, an electron injection layer 2107 having a thickness of 20 nm is used by a total of The electron transport layer 2106 is formed by evaporating ginseng (5-quinoline) complex aluminum (abbreviation: Alq) and lithium. Here, the weight ratio between Alq and lithium was adjusted to 1:0.01 (=Alq: lithium).
接著,具有厚度200萘米的第二個電極2108係藉由使用耐熱的蒸發法而形成於電子注射層2107上。因此,製造發光元件2。 Next, a second electrode 2108 having a thickness of 200 nm is formed on the electron injection layer 2107 by a heat-resistant evaporation method. Therefore, the light-emitting element 2 is manufactured.
圖39顯示發光元件2的電流密度對亮度特性,圖40顯示其電壓對亮度特性及圖41顯示其亮度對電流效率特性。再者,圖42顯示在1毫安培電流下所獲得的發射光譜。發光元件2在895cd/平方公尺之亮度下的CIE色度座標為(x=0.17,y=0.20)及發光為藍色。在895cd/平方公尺之亮度下的電流效率為4.4cd/安培,且同時電壓為5.8伏特及電流密度為20.1毫安培/平方公分。另外,如圖42所示,在1毫安培電流下的最大發射波長為443奈米。 Fig. 39 shows current density versus luminance characteristics of the light-emitting element 2, Fig. 40 shows its voltage versus luminance characteristics, and Fig. 41 shows its luminance versus current efficiency characteristics. Again, Figure 42 shows the emission spectra obtained at a current of 1 milliamperes. The CIE chromaticity coordinates of the light-emitting element 2 at a luminance of 895 cd/m 2 are (x = 0.17, y = 0.20) and the luminescence is blue. The current efficiency at a luminance of 895 cd/m 2 was 4.4 cd/ampere, and at the same time, the voltage was 5.8 volts and the current density was 20.1 mA/cm 2 . In addition, as shown in FIG. 42, the maximum emission wavelength at a current of 1 milliamperes is 443 nm.
本發明的發光元件以參考圖55被敘述於此具體實施例中。用於製造此具體實施例的發光元件之方法顯示於下。 The light-emitting element of the present invention is described in this specific embodiment with reference to FIG. The method for producing the light-emitting element of this embodiment is shown below.
首先,將含有氧化矽的氧化銦錫(ITSO)藉由濺鍍法沉積在玻璃基板2101上,得以形成第一個電極2102。應注意其厚度為110奈米及電極面積為2奈米x 2奈米。 First, indium tin oxide (ITSO) containing ruthenium oxide is deposited on the glass substrate 2101 by sputtering to form the first electrode 2102. It should be noted that the thickness is 110 nm and the electrode area is 2 nm x 2 nm.
接著,將於其上形成第一個電極的基板固定於真空蒸 發裝置中提供的基板固定架上,以該方式使得基板表面具有面朝下的第一個電極。將電壓減低至約10-4帊斯卡,並接著將4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)及氧化鉬(VI)共同蒸發在第一個電極2102上,藉此形成含有有機化合物與無機化合物之複合材料的層2103。層2103的膜厚度為50奈米,並且介於NPB與氧化鉬(VI)之間的重量比被設定為4:1(=NPB:氧化鉬)。應注意共同蒸發法為其中蒸發係在一個處理室中同時以數個蒸發源進行的蒸發方法。 Next, the substrate on which the first electrode is formed is fixed to the substrate holder provided in the vacuum evaporation apparatus in such a manner that the surface of the substrate has the first electrode facing downward. The voltage is reduced to about 10 -4 Å, and then 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB) and molybdenum oxide (VI) are common. Evaporation is performed on the first electrode 2102, thereby forming a layer 2103 containing a composite material of an organic compound and an inorganic compound. The film thickness of the layer 2103 was 50 nm, and the weight ratio between NPB and molybdenum oxide (VI) was set to 4:1 (= NPB: molybdenum oxide). It should be noted that the co-evaporation method is an evaporation method in which an evaporation system is carried out in one processing chamber while being performed by several evaporation sources.
接著,具有厚度10萘米的電洞傳輸層2104係藉由使用耐熱的蒸發法使用4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)而形成於含有複合材料的層2103上。 Next, the hole transport layer 2104 having a thickness of 10 nm is used by using a heat-resistant evaporation method using 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB). It is formed on the layer 2103 containing the composite material.
再者,具有厚度30萘米的發光層2105係藉由共同蒸發以結構式(20)代表的9-(4-第三丁苯基)-10-〔4-(咔唑-9-基)〕苯蒽(縮寫:PTBCzPA)及N,N’-雙〔4-(9H-咔唑-9-基)苯基〕-N,N’-二苯茋-4,4’-二胺(縮寫:YGA2S)而形成於電洞傳輸層2104上。在此介於PPCzPA與YGA2S之間的重量比被調整為1:0.05(=PTBCzPA:YGA2S)。 Further, the light-emitting layer 2105 having a thickness of 30 nm is a 9-(4-t-butylphenyl)-10-[4-(carbazol-9-yl) represented by the structural formula (20) by co-evaporation. Benzoquinone (abbreviation: PTBCzPA) and N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylindole-4,4'-diamine (abbreviation :YGA2S) is formed on the hole transport layer 2104. Here, the weight ratio between PPCzPA and YGA2S was adjusted to 1:0.05 (=PTBCzPA:YGA2S).
接著,具有厚度10萘米的電子傳輸層2106係藉由使用耐熱的蒸發法使用參(5-喹啉)絡鋁(縮寫:Alq)而形成於發光層2105上。 Next, an electron transport layer 2106 having a thickness of 10 nm was formed on the light-emitting layer 2105 by using a heat-resistant evaporation method using quinone (5-quinoline) complex aluminum (abbreviation: Alq).
而且,具有厚度20萘米的電子注射層2107係藉由共 同蒸發參(5-喹啉)絡鋁(縮寫:Alq)及鋰而形成於電子傳輸層2106。在此介於Alq與鋰之間的重量比被調整為1:0.01(=Alq:鋰)。 Moreover, an electron injection layer 2107 having a thickness of 20 nm is used by a total of The electron transport layer 2106 is formed by evaporating ginseng (5-quinoline) complex aluminum (abbreviation: Alq) and lithium. Here, the weight ratio between Alq and lithium was adjusted to 1:0.01 (=Alq: lithium).
接著,具有厚度200萘米的第二個電極2108係藉由使用耐熱的蒸發法而形成於電子注射層2107上。因此,製造發光元件3。 Next, a second electrode 2108 having a thickness of 200 nm is formed on the electron injection layer 2107 by a heat-resistant evaporation method. Therefore, the light-emitting element 3 is manufactured.
圖43顯示發光元件3的電流密度對亮度特性,圖44顯示其電壓對亮度特性及圖45顯示其亮度對電流效率特性。再者,圖46顯示在1毫安培電流下所獲得的發射光譜。發光元件3在1025cd/平方公尺之亮度下的CIE色度座標為(x=0.16,y=0.16)及發光為藍色。在1025cd/平方公尺之亮度下的電流效率為2.2cd/安培,且同時電壓為6.2伏特及電流密度為46.4毫安培/平方公分。另外,如圖46所示,在1毫安培電流下的最大發射波長為442奈米。 Fig. 43 shows current density versus luminance characteristics of the light-emitting element 3, Fig. 44 shows its voltage-to-luminance characteristic, and Fig. 45 shows its luminance versus current efficiency characteristics. Again, Figure 46 shows the emission spectra obtained at a current of 1 milliamperes. The CIE chromaticity coordinates of the light-emitting element 3 at a luminance of 1025 cd/m 2 are (x = 0.16, y = 0.16) and the luminescence is blue. The current efficiency at a luminance of 1025 cd/m 2 was 2.2 cd/ampere, and the voltage was 6.2 volts at the same time and the current density was 46.4 mA/cm 2 . In addition, as shown in Fig. 46, the maximum emission wavelength at a current of 1 milliamperes was 442 nm.
本發明的發光元件以參考圖55被敘述於此具體實施例中。用於製造此具體實施例的發光元件之方法顯示於下。 The light-emitting element of the present invention is described in this specific embodiment with reference to FIG. The method for producing the light-emitting element of this embodiment is shown below.
首先,將含有氧化矽的氧化銦錫(ITSO)藉由濺鍍法沉積在玻璃基板2101上,得以形成第一個電極2102。應注意其厚度為110奈米及電極面積為2奈米x 2奈米。 First, indium tin oxide (ITSO) containing ruthenium oxide is deposited on the glass substrate 2101 by sputtering to form the first electrode 2102. It should be noted that the thickness is 110 nm and the electrode area is 2 nm x 2 nm.
接著,將於其上形成第一個電極的基板固定於真空蒸 發裝置中提供的基板固定架上,以該方式使得基板表面具有面朝下的第一個電極。將電壓減低至約10-4帕斯卡,並接著將4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)及氧化鉬(VI)共同蒸發在第一個電極2102上,藉此形成含有有機化合物與無機化合物之複合材料的層2103。層2103的膜厚度為50奈米,並且介於NPB與氧化鉬(VI)之間的重量比被設定為4:1(=NPB:氧化鉬)。應注意共同蒸發法為其中蒸發係在一個處理室中同時以數個蒸發源進行的蒸發方法。 Next, the substrate on which the first electrode is formed is fixed to the substrate holder provided in the vacuum evaporation apparatus in such a manner that the surface of the substrate has the first electrode facing downward. The voltage is reduced to about 10 -4 Pascals, and then 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB) and molybdenum oxide (VI) are co-evaporated. On the first electrode 2102, a layer 2103 comprising a composite material of an organic compound and an inorganic compound is formed. The film thickness of the layer 2103 was 50 nm, and the weight ratio between NPB and molybdenum oxide (VI) was set to 4:1 (= NPB: molybdenum oxide). It should be noted that the co-evaporation method is an evaporation method in which an evaporation system is carried out in one processing chamber while being performed by several evaporation sources.
接著,具有厚度10萘米的電洞傳輸層2104係藉由使用耐熱的蒸發法使用4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)而形成於含有複合材料的層2103上。 Next, the hole transport layer 2104 having a thickness of 10 nm is used by using a heat-resistant evaporation method using 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB). It is formed on the layer 2103 containing the composite material.
再者,具有厚度30萘米的發光層2105係藉由共同蒸發以結構式(16)代表的9-〔4-(咔唑-9-基)苯基〕-10-(2-萘基)蒽(縮寫:β NCzPA)及N,N’-雙〔4-(9H-咔唑-9-基)苯基〕-N,N’-二苯茋-4,4’-二胺(縮寫:YGA2S)而形成於電洞傳輸層2104上。在此介於β NCzPA與YGA2S之間的重量比被調整為1:0.05(=β NCzPA:YGA2S)。 Further, the light-emitting layer 2105 having a thickness of 30 nm is a 9-[4-(carbazol-9-yl)phenyl]-10-(2-naphthyl) group represented by the structural formula (16) by co-evaporation.蒽 (abbreviation: β NCzPA) and N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylindole-4,4'-diamine (abbreviation: YGA2S) is formed on the hole transport layer 2104. Here, the weight ratio between β NCzPA and YGA 2S was adjusted to 1:0.05 (=β NCzPA:YGA2S).
接著,具有厚度10萘米的電子傳輸層2106係藉由使用耐熱的蒸發法使用參(5-喹啉)絡鋁(縮寫:Alq)而形成於發光層2105上。 Next, an electron transport layer 2106 having a thickness of 10 nm was formed on the light-emitting layer 2105 by using a heat-resistant evaporation method using quinone (5-quinoline) complex aluminum (abbreviation: Alq).
而且,具有厚度20萘米的電子注射層2107係藉由共 同蒸發參(5-喹啉)絡鋁(縮寫:Alq)及鋰而形成於電子傳輸層2106。在此介於Alq與鋰之間的重量比被調整為1:0.01(=Alq:鋰)。 Moreover, an electron injection layer 2107 having a thickness of 20 nm is used by a total of The electron transport layer 2106 is formed by evaporating ginseng (5-quinoline) complex aluminum (abbreviation: Alq) and lithium. Here, the weight ratio between Alq and lithium was adjusted to 1:0.01 (=Alq: lithium).
接著,具有厚度200萘米的第二個電極2108係藉由使用耐熱的蒸發法而形成於電子注射層2107上。因此,製造發光元件4。 Next, a second electrode 2108 having a thickness of 200 nm is formed on the electron injection layer 2107 by a heat-resistant evaporation method. Therefore, the light-emitting element 4 is manufactured.
圖47顯示發光元件4的電流密度對亮度特性,圖48顯示其電壓對亮度特性及圖49顯示其亮度對電流效率特性。再者,圖50顯示在1毫安培電流下所獲得的發射光譜。發光元件4在938cd/平方公尺之亮度下的CIE色度座標為(x=0.18,y=0.22)及發光為藍色。在938cd/平方公尺之亮度下的電流效率為4.3cd/安培,且同時電壓為6.0伏特及電流密度為21.9毫安培/平方公分。另外,如圖50所示,在1毫安培電流下的最大發射波長為445奈米。 Fig. 47 shows the current density versus luminance characteristics of the light-emitting element 4, Fig. 48 shows its voltage versus luminance characteristics, and Fig. 49 shows its luminance versus current efficiency characteristics. Again, Figure 50 shows the emission spectra obtained at a current of 1 milliamperes. The CIE chromaticity coordinates of the light-emitting element 4 at a luminance of 938 cd/m 2 are (x = 0.18, y = 0.22) and the luminescence is blue. The current efficiency at a luminance of 938 cd/m 2 was 4.3 cd/ampere, and at the same time, the voltage was 6.0 volts and the current density was 21.9 mA/cm 2 . In addition, as shown in FIG. 50, the maximum emission wavelength at a current of 1 milliamperes is 445 nm.
本發明的發光元件以參考圖55被敘述於此具體實施例中。用於製造此具體實施例的發光元件之方法顯示於下。 The light-emitting element of the present invention is described in this specific embodiment with reference to FIG. The method for producing the light-emitting element of this embodiment is shown below.
首先,將含有氧化矽的氧化銦錫(ITSO)藉由濺鍍法沉積在玻璃基板2101上,得以形成第一個電極2102。應注意其厚度為110奈米及電極面積為2奈米x 2奈米。 First, indium tin oxide (ITSO) containing ruthenium oxide is deposited on the glass substrate 2101 by sputtering to form the first electrode 2102. It should be noted that the thickness is 110 nm and the electrode area is 2 nm x 2 nm.
接著,將於其上形成第一個電極的基板固定於真空蒸 發裝置中提供的基板固定架上,以該方式使得基板表面具有面朝下的第一個電極。將電壓減低至約10-4帊斯卡,並接著將4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)及氧化鉬(VI)共同蒸發在第一個電極2102上,藉此形成含有有機化合物與無機化合物之複合材料的層2103。層2103的膜厚度為50奈米,並且介於NPB與氧化鉬(VI)之間的重量比被設定為4:1(=NPB:氧化鉬)。應注意共同蒸發法為其中蒸發係在一個處理室中同時以數個蒸發源進行的蒸發方法。 Next, the substrate on which the first electrode is formed is fixed to the substrate holder provided in the vacuum evaporation apparatus in such a manner that the surface of the substrate has the first electrode facing downward. The voltage is reduced to about 10 -4 Å, and then 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB) and molybdenum oxide (VI) are common. Evaporation is performed on the first electrode 2102, thereby forming a layer 2103 containing a composite material of an organic compound and an inorganic compound. The film thickness of the layer 2103 was 50 nm, and the weight ratio between NPB and molybdenum oxide (VI) was set to 4:1 (= NPB: molybdenum oxide). It should be noted that the co-evaporation method is an evaporation method in which an evaporation system is carried out in one processing chamber while being performed by several evaporation sources.
接著,具有厚度10萘米的電洞傳輸層2104係藉由使用耐熱的蒸發法使用4,4’-雙〔N-(1-萘基)-N-苯胺基〕聯苯(縮寫:NPB)而形成於含有複合材料的層2103上。 Next, the hole transport layer 2104 having a thickness of 10 nm is used by using a heat-resistant evaporation method using 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl (abbreviation: NPB). It is formed on the layer 2103 containing the composite material.
再者,具有厚度30萘米的發光層2105係藉由共同蒸發以結構式(42)代表的9-〔4-(咔唑-9-基)苯基〕-10-(4-三氟甲基苯基)蒽(縮寫:CF3CzPA)及N,N’-雙〔4-(9H-咔唑-9-基)苯基〕-N,N’-二苯茋-4,4’-二胺(縮寫:YGA2S)而形成於電洞傳輸層2104上。在此介於PPCzPA與YGA2S之間的重量比被調整為1:0.05(=PPCzPA:YGA2S)。 Further, the light-emitting layer 2105 having a thickness of 30 nm is a 9-[4-(carbazol-9-yl)phenyl]-10-(4-trifluoromethyl) represented by the structural formula (42) by co-evaporation. Phenyl) hydrazine (abbreviation: CF3CzPA) and N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylindole-4,4'-diamine (abbreviation: YGA2S) is formed on the hole transport layer 2104. Here, the weight ratio between PPCzPA and YGA2S was adjusted to 1:0.05 (=PPCzPA: YGA2S).
接著,具有厚度10萘米的電子傳輸層2106係藉由使用耐熱的蒸發法使用參(5-喹啉)絡鋁(縮寫:Alq)而形成於發光層2105上。 Next, an electron transport layer 2106 having a thickness of 10 nm was formed on the light-emitting layer 2105 by using a heat-resistant evaporation method using quinone (5-quinoline) complex aluminum (abbreviation: Alq).
而且,具有厚度20萘米的電子注射層2107係藉由共 同蒸發參(5-喹啉)絡鋁(縮寫:Alq)及鋰而形成於電子傳輸層2106。在此介於Alq與鋰之間的重量比被調整為1:0.01(=Alq:鋰)。 Moreover, an electron injection layer 2107 having a thickness of 20 nm is used by a total of The electron transport layer 2106 is formed by evaporating ginseng (5-quinoline) complex aluminum (abbreviation: Alq) and lithium. Here, the weight ratio between Alq and lithium was adjusted to 1:0.01 (=Alq: lithium).
接著,具有厚度200萘米的第二個電極2108係藉由使用耐熱的蒸發法而形成於電子注射層2107上。因此,製造發光元件5。 Next, a second electrode 2108 having a thickness of 200 nm is formed on the electron injection layer 2107 by a heat-resistant evaporation method. Therefore, the light-emitting element 5 is manufactured.
圖51顯示發光元件5的電流密度對亮度特性,圖52顯示其電壓對亮度特性及圖53顯示其亮度對電流效率特性。再者,圖54顯示在1毫安培電流下所獲得的發射光譜。發光元件5在907cd/平方公尺之亮度下的CIE色度座標為(x=0.20,y=0.33)及發光為藍色。在907cd/平方公尺之亮度下的電流效率為4.5cd/安培,且同時電壓為6.8伏特及電流密度為20.3毫安培/平方公分。另外,如圖54所示,在1毫安培電流下的最大發射波長為497奈米。 Fig. 51 shows the current density versus luminance characteristics of the light-emitting element 5, Fig. 52 shows its voltage versus luminance characteristics, and Fig. 53 shows its luminance versus current efficiency characteristics. Again, Figure 54 shows the emission spectra obtained at a current of 1 milliamperes. The CIE chromaticity coordinates of the light-emitting element 5 at a luminance of 907 cd/m 2 are (x = 0.20, y = 0.33) and the luminescence is blue. The current efficiency at a luminance of 907 cd/m 2 was 4.5 cd/ampere, and at the same time, the voltage was 6.8 volts and the current density was 20.3 mA/cm 2 . In addition, as shown in Fig. 54, the maximum emission wavelength at a current of 1 milliamperes was 497 nm.
本申請案係以在2006年8月30日於日本專利局提出申請的日本專利申請序號2006-234639為基準,將其整個內容併入本文以供參考。 The present application is based on Japanese Patent Application No. 2006-234639, filed on Jan.
101‧‧‧基板 101‧‧‧Substrate
102‧‧‧第一個電極 102‧‧‧first electrode
103‧‧‧第一層 103‧‧‧ first floor
104‧‧‧第二層 104‧‧‧ second floor
105‧‧‧第三層 105‧‧‧ third floor
106‧‧‧第四層 106‧‧‧ fourth floor
107‧‧‧第二個電極 107‧‧‧Second electrode
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2007
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- 2007-08-22 CN CN2007800316623A patent/CN101506163B/en not_active Expired - Fee Related
- 2007-08-27 US US11/845,432 patent/US20080107918A1/en not_active Abandoned
- 2007-08-28 TW TW096131873A patent/TWI488842B/en not_active IP Right Cessation
- 2007-08-28 TW TW104111434A patent/TWI680120B/en not_active IP Right Cessation
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WO2008026614A1 (en) | 2008-03-06 |
US8183793B2 (en) | 2012-05-22 |
US20110050118A1 (en) | 2011-03-03 |
TW200825052A (en) | 2008-06-16 |
CN101506163A (en) | 2009-08-12 |
TWI488842B (en) | 2015-06-21 |
US20080107918A1 (en) | 2008-05-08 |
TWI680120B (en) | 2019-12-21 |
CN101506163B (en) | 2012-05-02 |
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